WorldWideScience

Sample records for asymmetric total synthesis

  1. Asymmetric total synthesis of vindoline.

    Science.gov (United States)

    Kato, Daisuke; Sasaki, Yoshikazu; Boger, Dale L

    2010-03-24

    A concise asymmetric total synthesis of (-)-vindoline (1) is detailed based on a tandem intramolecular [4+2]/[3+2] cycloaddition cascade of a 1,3,4-oxadiazole inspired by the natural product structure, in which the tether linking the initiating dienophile and oxadiazole bears a chiral substituent that controls the facial selectivity of the initiating Diels-Alder reaction and sets absolute stereochemistry of the remaining six stereocenters in the cascade cycloadduct. This key reaction introduces three rings and four C-C bonds central to the pentacyclic ring system setting all six stereocenters and introducing essentially all the functionality found in the natural product in a single step. Implementation of the approach also required the development of a unique ring expansion reaction to provide a six-membered ring suitably functionalized for introduction of the Delta (6, 7)-double bond found in the core structure of vindoline and defined our use of a protected hydroxymethyl group as the substituent used to control the stereochemical course of the cycloaddition cascade.

  2. Asymmetric Total Synthesis of (-)-Cladospolide B

    Institute of Scientific and Technical Information of China (English)

    WANG,Wen-Kuan; ZHANG,Ji-Yong; HE,Jin-Mei; TANG,Shi-Bing; WANG,Xiao-Lei; SHE,Xue-Gong; PAN,Xin-Fu

    2008-01-01

    An enantioselective total synthesis of (-)-cladospolide B was described.The key steps in this synthesis include (a) a Sharpless asymmetric dihydroxylation to elaborate syn diol at C-4 and C-5 positions;(b) a Mitsunobu esterification to reverse the configuration at C-11 from (S) to (R);and (c) a ring-closing metathesis to access the 12-membered macrocyclic ring.

  3. Catalytic Asymmetric Total Synthesis of Hedyosumins A, B, and C.

    Science.gov (United States)

    Sun, Wang-Bin; Wang, Xuan; Sun, Bing-Feng; Zou, Jian-Ping; Lin, Guo-Qiang

    2016-03-18

    The first and asymmetric total synthesis of hedyosumins A, B, and C was accomplished in 13-14 steps from simple starting materials. The essential tools that allow us to access the tetracyclic skeleton include an organocatalytic [4 + 3] cycloaddition reaction, an intramolecular aldol condensation, and an intramolecular carboxymercuration/demercuration enabled lactonization. A CBS-catalyzed asymmetric reduction was employed to boost the ee of the synthetic natural products to an excellent level. This synthesis established the absolute configurations of hedyosumins A, B, and C. PMID:26925758

  4. Asymmetric Total Synthesis of a Diastereisomer A of Tuxpanolide

    Institute of Scientific and Technical Information of China (English)

    WANG,Jin-Xin; ZHANG,Chao-Xin; LI,Ying

    2004-01-01

    @@ α-Alkylidene-β-hydroxy butyrolactones have been attractive and challenging targets for organic synthesis in various laboratories because that not only they are rich in skeletal diversity and stereochemistry complexity but also many of them possess quite intriguing and wide biological activities.[1] A novel class of the phytane-type diterpenoid named Tuxpanolide, bearing α-alkylidene-β-hydroxy-γ-butyrolactone skeleton, was isolated from Perymenium hintonii in Central Mexico by Maldonado and co-wokers in 1998.[2] Now we firstly report the efficient strategy of the stereocontrolled total synthesis of a diastereisomer A of Tuxpanolide.

  5. Substrate-Controlled Asymmetric Total Synthesis and Structure Revision of (-)-Bisezakyne A.

    Science.gov (United States)

    Shin, Iljin; Lee, Dongjoo; Kim, Hyoungsu

    2016-09-01

    The first asymmetric total synthesis and subsequent structure revision of (-)-bisezakyne A, a Laurencia C15 acetogenin from Alpysia oculifera, has been accomplished. Our substrate-controlled synthesis of this oxolane natural product features a highly stereoselective "protecting-group-dependent" intramolecular amide enolate alkylation strategy for the synthesis of the key 9,10-trans-9,12-cis-10-hydroxytetrahydrofuran intermediate through "nonchelate" control. In addition, our synthesis determined the absolute configuration of the halogenated marine natural product. PMID:27551943

  6. Total Synthesis of Chiral Biaryl Natural Products by Asymmetric Biaryl Coupling ‡

    OpenAIRE

    Kozlowski, Marisa C.; Morgan, Barbara J.; Linton, Elizabeth C.

    2009-01-01

    This tutorial review highlights the use of catalytic asymmetric 2-naphthol couplings in total synthesis. The types of chirality, chiral biaryl natural products, prior approaches to chiral biaryl natural products, and other catalytic asymmetric biaryl couplings are outlined. The three main categories of chiral catalysts for 2-naphthol coupling (Cu, V, Fe) are described with discussion of their limitations and advantages. Applications of the copper catalyzed couplings in biomimetic syntheses ar...

  7. Asymmetric Total Synthesis of the Indole Diterpene Alkaloid Paspaline.

    Science.gov (United States)

    Sharpe, Robert J; Johnson, Jeffrey S

    2015-10-01

    An enantioselective synthesis of the indole diterpenoid natural product paspaline is disclosed. Critical to this approach was the implementation of stereoselective desymmetrization reactions to assemble key stereocenters of the molecule. The design and execution of these tactics are described in detail, and a thorough analysis of observed outcomes is presented, ultimately providing the title compound in high stereopurity. This synthesis provides a novel template for preparing key stereocenters in this family of molecules, and the reactions developed en route to paspaline present a series of new synthetic disconnections in preparing steroidal natural products.

  8. Asymmetric synthesis v.4

    CERN Document Server

    Morrison, James

    1984-01-01

    Asymmetric Synthesis, Volume 4: The Chiral Carbon Pool and Chiral Sulfur, Nitrogen, Phosphorus, and Silicon Centers describes the practical methods of obtaining chiral fragments. Divided into five chapters, this book specifically examines initial chiral transmission and extension. The opening chapter describes the so-called chiral carbon pool, the readily available chiral carbon fragments used as building blocks in synthesis. This chapter also provides a list of 375 chiral building blocks, along with their commercial sources, approximate prices, and methods of synthesis. Schemes involving

  9. Catalytic asymmetric synthesis of mycocerosic acid

    NARCIS (Netherlands)

    ter Horst, B.; Feringa, B.L.; J. Minnaard, A.

    2007-01-01

    The first catalytic asymmetric total synthesis of mycocerosic acid was achieved via the application of iterative enantioselective 1,4-addition reactions and allows for the efficient construction of 1,3-polymethyl arrays with full stereocontrol; further exemplified by the synthesis of tetramethyl-dec

  10. Total synthesis of ochnaflavone

    OpenAIRE

    Monica M. Ndoile; van Heerden, Fanie R

    2013-01-01

    The first total syntheses of ochnaflavone, an asymmetric biflavone consisting of apigenin and luteolin moieties, and the permethyl ether of 2,3,2'',3''-tetrahydroochnaflavone have been achieved. The key steps in the synthesis of ochnaflavone were the formation of a diaryl ether and ring cyclization of an ether-linked dimeric chalcone to assemble the two flavone nuclei. Optimal experimental conditions for the oxidative cyclization to form ochnaflavone were established.

  11. Total synthesis of ochnaflavone

    Directory of Open Access Journals (Sweden)

    Monica M. Ndoile

    2013-07-01

    Full Text Available The first total syntheses of ochnaflavone, an asymmetric biflavone consisting of apigenin and luteolin moieties, and the permethyl ether of 2,3,2'',3''-tetrahydroochnaflavone have been achieved. The key steps in the synthesis of ochnaflavone were the formation of a diaryl ether and ring cyclization of an ether-linked dimeric chalcone to assemble the two flavone nuclei. Optimal experimental conditions for the oxidative cyclization to form ochnaflavone were established.

  12. Concise Asymmetric Construction of C2 -symmetric 1,9-Diarylnonanoids Using a Hypervalent Silicon Complex: Total Synthesis of (-)-Ericanone.

    Science.gov (United States)

    Kotani, Shunsuke; Kai, Kosuke; Shimoda, Yasushi; Hu, Hao; Gao, Shen; Sugiura, Masaharu; Ogasawara, Masamichi; Nakajima, Makoto

    2016-02-01

    By using a phosphine oxide-catalyzed enantioselective double aldol reaction, we achieved the concise construction of C2 -symmetric 1,9-diarylnonanoids, enabling the synthesis of (-)-ericanone from p-hydroxybenzaldehyde in 6 steps with 65 % overall yield. The enantioselective double aldol reaction is useful for establishing C2 -symmetric 1,9-diaryl-3,7-dihydroxy-5-nonanones with a single operation. Furthermore, the use of o-nosyl-protected p-hydroxybenzaldehyde and a 4,4'-disubstituted BINAP dioxide catalyst dramatically improved the reactivity and selectivity in the double aldol reaction, enabling the total synthesis of (-)-ericanone with high yield and with excellent enantiopurity.

  13. 1,6-asymmetric induction in boron-mediated aldol reactions: application to a practical total synthesis of (+)-discodermolide.

    Science.gov (United States)

    Paterson, Ian; Delgado, Oscar; Florence, Gordon J; Lyothier, Isabelle; Scott, Jeremy P; Sereinig, Natascha

    2003-01-01

    By relying solely on substrate-based stereocontrol, a practical total synthesis of the microtubule-stabilizing anticancer agent (+)-discodermolide has been realized. This exploits a novel aldol bond construction with 1,6-stereoinduction from the boron enolate of (Z)-enone 3 in addition to aldehyde 2. The 1,3-diol 7 is employed as a common building block for the C(1)-C(5), C(9)-C(16), and C(17)-C(24) subunits. [reaction--see text

  14. Total Synthesis of (-)-Daphenylline.

    Science.gov (United States)

    Yamada, Ryosuke; Adachi, Yohei; Yokoshima, Satoshi; Fukuyama, Tohru

    2016-05-10

    Total synthesis of (-)-daphenylline, a hexacyclic Daphniphyllum alkaloid, was achieved. Construction of the tricyclic DEF ring system was initiated by asymmetric Negishi coupling followed by an intramolecular Friedel-Crafts reaction. Installation of a side chain onto the tricyclic core was carried out through Sonogashira coupling, stereocontrolled Claisen rearrangement by taking advantage of the characteristic conformation of the tricyclic DEF core, and the stereoselective alkylation of a lactone. After the introduction of a glycine unit, the ABC ring system was stereoselectively constructed through intramolecular cycloaddition of the cyclic azomethine ylide. PMID:27062676

  15. Asymmetric Formal Synthesis of Azadirachtin.

    Science.gov (United States)

    Mori, Naoki; Kitahara, Takeshi; Mori, Kenji; Watanabe, Hidenori

    2015-12-01

    An asymmetric formal synthesis of azadirachtin, a potent insect antifeedant, was accomplished in 30 steps to Ley's synthetic intermediate (longest linear sequence). The synthesis features: 1) rapid access to the optically active right-hand segment starting from the known 5-hydroxymethyl-2-cyclopentenone scaffold; 2) construction of the B and E rings by a key intramolecular tandem radical cyclization; 3) formation of the hemiacetal moiety in the C ring through the α-oxidation of the six-membered lactone followed by methanolysis. PMID:26474211

  16. Cyclodextrins in Asymmetric and Stereospecific Synthesis

    Directory of Open Access Journals (Sweden)

    Fliur Macaev

    2015-09-01

    Full Text Available Since their discovery, cyclodextrins have widely been used as green and easily available alternatives to promoters or catalysts of different chemical reactions in water. This review covers the research and application of cyclodextrins and their derivatives in asymmetric and stereospecific syntheses, with their division into three main groups: (1 cyclodextrins promoting asymmetric and stereospecific catalysis in water; (2 cyclodextrins’ complexes with transition metals as asymmetric and stereospecific catalysts; and (3 cyclodextrins’ non-metallic derivatives as asymmetric and stereospecific catalysts. The scope of this review is to systematize existing information on the contribution of cyclodextrins to asymmetric and stereospecific synthesis and, thus, to facilitate further development in this direction.

  17. Asymmetric Synthesis via Chiral Aziridines

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Harden, Adrian; Wyatt, Paul;

    1996-01-01

    A series of chiral bis(aziridines) has been synthesised and evaluated as chelating ligands for a variety of asymmetric transformations mediated by metals [Os (dihydroxylation), Pd (allylic alkylation) Cu (cyclopropanation and aziridination, Li (1,2-addition of organolithiums to imines)]. In the b......A series of chiral bis(aziridines) has been synthesised and evaluated as chelating ligands for a variety of asymmetric transformations mediated by metals [Os (dihydroxylation), Pd (allylic alkylation) Cu (cyclopropanation and aziridination, Li (1,2-addition of organolithiums to imines...

  18. Total synthesis of aeruginosin 98B.

    Science.gov (United States)

    Trost, Barry M; Kaneko, Toshiyuki; Andersen, Neil G; Tappertzhofen, Christoph; Fahr, Bruce

    2012-11-21

    The first total synthesis of aeruginosin 98B was accomplished. The key step is a highly diastereoselective Pd-catalyzed intramolecular asymmetric allylic alkylation reaction of a diastereomeric mixture of allylic carbonates that is enabled by the use of racemic phosphine ligand L1.

  19. Synthesis of Asymmetric Propanetriol Analogues

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    From natural tartaric acid, (R)-2-benzyloxy-3-(2-tetrahydropyranyloxy) propanol 3 was designed and synthesized, and (R)-2-benzyloxy-3-(4-methoxybenzyloxy) propanol 7 was prepared in a new method. They can be used as chiral synthons of lysophosphatidic acid and other compounds with asymmetric propanetriol backbone.

  20. Total synthesis of atropurpuran.

    Science.gov (United States)

    Gong, Jing; Chen, Huan; Liu, Xiao-Yu; Wang, Zhi-Xiu; Nie, Wei; Qin, Yong

    2016-01-01

    Due to their architectural intricacy and biological significance, the synthesis of polycyclic diterpenes and their biogenetically related alkaloids have been the subject of considerable interest over the last few decades, with progress including the impressive synthesis of several elusive targets. Despite tremendous efforts, conquering the unique structural types of this large natural product family remains a long-term challenge. The arcutane diterpenes and related alkaloids, bearing a congested tetracyclo[5.3.3.0(4,9).0(4,12)]tridecane unit, are included in these unsolved enigmas. Here we report a concise approach to the construction of the core structure of these molecules and the first total synthesis of (±)-atropurpuran. Pivotal features of the synthesis include an oxidative dearomatization/intramolecular Diels-Alder cycloaddition cascade, sequential aldol and ketyl-olefin cyclizations to assemble the highly caged framework, and a chemoselective and stereoselective reduction to install the requisite allylic hydroxyl group in the target molecule. PMID:27387707

  1. Total Synthesis of Naloxone

    Institute of Scientific and Technical Information of China (English)

    HU Wen-Xiang; WANG Jian-Ying; XU Ming

    2003-01-01

    @@ Naloxone (1) is one of the 14-hydroxyl substituted opium antagonists which are valuable medications for treat ment of opiate abuse, opiate overdose, and alcohol addiction. Here, the total synthesis of naloxone was described. We selected 2,6-dihydroxynaphalene (2) as the starting material.

  2. Power spectra of a constrained totally asymmetric simple exclusion process

    Science.gov (United States)

    Cook, L. Jonathan; Zia, R. K. P.

    2010-07-01

    In nature, all biological systems function in a far-from-equilibrium state. Here, we study the process of translation in protein synthesis, using the totally asymmetric simple exclusion process (TASEP) as a model. In particular, we explore the effects of a finite supply of particles for the TASEP, as in a living cell with a finite pool of ribosomes. Specifically, we investigate the power spectrum associated with total occupancy, utilizing both Monte Carlo simulations and theoretical analysis. New features arise, such as large suppressions at low frequencies, due to the added constraint. A theory is formulated based on a Langevin approach with discrete space and time. With good agreement between the simulation and theory, we gain some insights into the effects of finite resources on the TASEP.

  3. Total Synthesis of Millingtonine.

    Science.gov (United States)

    Brown, Patrick D; Lawrence, Andrew L

    2016-07-11

    Millingtonine is a glycosidic alkaloid that exists as a pair of pseudo-enantiomeric diastereomers. Consideration of the likely biosynthetic origins of this unusual natural product has resulted in the development of a seven-step total synthesis. Results from this synthetic work provide evidence in support of a proposed network of biosynthetic pathways that can account for the formation of several phenylethanoid natural products. PMID:27249628

  4. Total synthesis of teixobactin

    Science.gov (United States)

    Jin, Kang; Sam, Iek Hou; Po, Kathy Hiu Laam; Lin, Du'an; Ghazvini Zadeh, Ebrahim H.; Chen, Sheng; Yuan, Yu; Li, Xuechen

    2016-08-01

    To cope with the global bacterial multidrug resistance, scientific communities have devoted significant efforts to develop novel antibiotics, particularly those with new modes of actions. Teixobactin, recently isolated from uncultured bacteria, is considered as a promising first-in-class drug candidate for clinical development. Herein, we report its total synthesis by a highly convergent Ser ligation approach and this strategy allows us to prepare several analogues of the natural product.

  5. Total synthesis of teixobactin.

    Science.gov (United States)

    Jin, Kang; Sam, Iek Hou; Po, Kathy Hiu Laam; Lin, Du'an; Ghazvini Zadeh, Ebrahim H; Chen, Sheng; Yuan, Yu; Li, Xuechen

    2016-01-01

    To cope with the global bacterial multidrug resistance, scientific communities have devoted significant efforts to develop novel antibiotics, particularly those with new modes of actions. Teixobactin, recently isolated from uncultured bacteria, is considered as a promising first-in-class drug candidate for clinical development. Herein, we report its total synthesis by a highly convergent Ser ligation approach and this strategy allows us to prepare several analogues of the natural product. PMID:27484680

  6. Asymmetric catalysis in organic synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Reilly, S.D.; Click, D.R.; Grumbine, S.K.; Scott, B.L.; Watkins, J.G.

    1998-11-01

    This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The goal of the project was to prepare new catalyst systems, which would perform chemical reactions in an enantioselective manner so as to produce only one of the possible optical isomers of the product molecule. The authors have investigated the use of lanthanide metals bearing both diolate and Schiff-base ligands as catalysts for the enantioselective reduction of prochiral ketones to secondary alcohols. The ligands were prepared from cheap, readily available starting materials, and their synthesis was performed in a ''modular'' manner such that tailoring of specific groups within the ligand could be carried out without repeating the entire synthetic procedure. In addition, they have developed a new ligand system for Group IV and lanthanide-based olefin polymerization catalysts. The ligand system is easily prepared from readily available starting materials and offers the opportunity to rapidly prepare a wide range of closely related ligands that differ only in their substitution patterns at an aromatic ring. When attached to a metal center, the ligand system has the potential to carry out polymerization reactions in a stereocontrolled manner.

  7. Catalytic asymmetric synthesis of biologically important 3-hydroxyoxindoles: an update

    Science.gov (United States)

    2016-01-01

    Summary Oxindole scaffolds are prevalent in natural products and have been recognized as privileged substructures in new drug discovery. Several oxindole-containing compounds have advanced into clinical trials for the treatment of different diseases. Among these compounds, enantioenriched 3-hydroxyoxindole scaffolds also exist in natural products and have proven to possess promising biological activities. A large number of catalytic asymmetric strategies toward the construction of 3-hydroxyoxindoles based on transition metal catalysis and organocatalysis have been reported in the last decades. Additionally, 3-hydroxyoxindoles as versatile precursors have also been used in the total synthesis of natural products and for constructing structurally novel scaffolds. In this review, we aim to provide an overview about the catalytic asymmetric synthesis of biologically important 3-substituted 3-hydroxyoxindoles and 3-hydroxyoxindole-based further transformations. PMID:27340490

  8. Total synthesis of the indolizidine alkaloid tashiromine

    Directory of Open Access Journals (Sweden)

    McElhinney Alison D

    2008-01-01

    Full Text Available Abstract Background Tashiromine 1 is a naturally occurring indolizidine alkaloid. It has been the subject of thirteen successful total syntheses to date. Our own approach centres on the stereoselective construction of the indolizidine core by capture of an electrophilic acyliminium species by a pendant allylsilane. The key cyclisation precursor is constructed using olefin cross-metathesis chemistry, which has the potential to facilitate both racemic and asymmetric approaches, depending upon the choice of the allylsilane metathesis partner. Results The use of the allyltrimethylsilane cross-metathesis approach enables the rapid construction of the key cyclisation precursor 3 (3 steps from commercial materials, which undergoes acid-induced cyclisation to give the desired bicyclic indolizidine skeleton as a 96:4 mixture of diastereomers. Simple functional group interconversions allowed the completion of the total synthesis of racemic tashiromine in six steps (19% overall yield. Three chiral α-alkoxyallylsilanes (12,14 and 15 were prepared in enantioenriched form and their cross-metathesis reactions studied as part of a putative asymmetric approach to tashiromine. In the event, α-hydroxysilane 12 underwent isomerisation under the reaction conditions to acylsilane 17, while silanes 14 and 15 were unreactive towards metathesis. Conclusion A concise, stereoselective total synthesis of racemic tashiromine has been developed. Attempts to translate this into an asymmetric synthesis have thus far been unsuccessful.

  9. Asymmetric Synthesis of Both Enantiomers of Disparlure

    Institute of Scientific and Technical Information of China (English)

    王志刚; 郑剑峰; 黄培强

    2012-01-01

    Starting from propargyl alcohol (12), and on the basis of Zhou's modified Sharpless asymmetric epoxidation, the sex pheromone of the Gypsy moth, disparlure (+)-8 and its enantiomer (-)-8 have been synthesized, each in six steps, with overall yields of 29% for (+)-8 and 27% for (-)-8 (ee〉98%). The use of the sequential coupling tactic renders the method flexible, which is applicable to the synthesis of other cis-epoxy pheromones.

  10. A novel and practical asymmetric synthesis of dapoxetine hydrochloride

    Directory of Open Access Journals (Sweden)

    Yijun Zhu

    2015-12-01

    Full Text Available A novel and practical asymmetric synthesis of dapoxetine hydrochloride by using the chiral auxiliary (S-tert-butanesulfinamide was explored. The synthesis was concise, mild, and easy to perform. The overall yield and stereoselectivity were excellent.

  11. Total Synthesis of Mycalolides A and B through Olefin Metathesis.

    Science.gov (United States)

    Kita, Masaki; Oka, Hirotaka; Usui, Akihiro; Ishitsuka, Tomoya; Mogi, Yuzo; Watanabe, Hidekazu; Tsunoda, Masaki; Kigoshi, Hideo

    2015-11-16

    An asymmetric total synthesis of the trisoxazole marine macrolides mycalolides A and B is described. This synthesis involves the convergent assembly of highly functionalized C1-C19 trisoxazole and C20-C35 side-chain segments through the use of olefin metathesis and esterification as well as Julia-Kocienski olefination and enamide formation as key steps. PMID:26450520

  12. Total Synthesis of Mycalolides A and B through Olefin Metathesis.

    Science.gov (United States)

    Kita, Masaki; Oka, Hirotaka; Usui, Akihiro; Ishitsuka, Tomoya; Mogi, Yuzo; Watanabe, Hidekazu; Tsunoda, Masaki; Kigoshi, Hideo

    2015-11-16

    An asymmetric total synthesis of the trisoxazole marine macrolides mycalolides A and B is described. This synthesis involves the convergent assembly of highly functionalized C1-C19 trisoxazole and C20-C35 side-chain segments through the use of olefin metathesis and esterification as well as Julia-Kocienski olefination and enamide formation as key steps.

  13. Asymmetric catalytic synthesis of the proposed structure of trocheliophorolide B.

    Science.gov (United States)

    Trost, Barry M; Quintard, Adrien

    2012-09-01

    A concise catalytic asymmetric synthesis of the proposed structure of trocheliophorolide B is reported. The synthetic sequence notably features an asymmetric acetaldehyde alkynylation, a Ru-catalyzed alder-ene reaction, and a Zn-ProPhenol ynone aldol condensation. Comparison with the reported data suggests a misassignment of the natural product structure.

  14. Asymmetric catalytic synthesis of the proposed structure of trocheliophorolide B

    OpenAIRE

    Trost, Barry M.; Quintard, Adrien

    2012-01-01

    A concise catalytic asymmetric synthesis of the proposed structure of Trocheliophorolide B is reported. The synthetic sequence notably features an asymmetric acetaldehyde alkynylation, Ru-catalyzed alder-ene reaction and Zn-ProPhenol ynone aldol condensation. Comparison with the reported data suggests a miss-assignment of the natural product structure.

  15. Asymmetric Synthesis of ( - ) -(2R, 3R, 6S ) -Irnigaine

    Institute of Scientific and Technical Information of China (English)

    MA, Nan; MA, Da-Wei

    2003-01-01

    Asymmetric synthesis of irnigaine was achieved starting from an enantiopure β-amino ester 5 using the condensation of amino alcohol 2 with acetylacetone and the subsequent intramolecular cyclization as the key steps.

  16. Catalytic Methods in Asymmetric Synthesis Advanced Materials, Techniques, and Applications

    CERN Document Server

    Gruttadauria, Michelangelo

    2011-01-01

    This book covers advances in the methods of catalytic asymmetric synthesis and their applications. Coverage moves from new materials and technologies to homogeneous metal-free catalysts and homogeneous metal catalysts. The applications of several methodologies for the synthesis of biologically active molecules are discussed. Part I addresses recent advances in new materials and technologies such as supported catalysts, supports, self-supported catalysts, chiral ionic liquids, supercritical fluids, flow reactors and microwaves related to asymmetric catalysis. Part II covers advances and milesto

  17. Diastereoselective Total Synthesis of (-)-Galiellalactone.

    Science.gov (United States)

    Kim, Taewoo; Han, Young Taek; An, Hongchan; Kim, Kyeojin; Lee, Jeeyeon; Suh, Young-Ger

    2015-12-18

    An enantioselective total synthesis of (-)-galiellalactone has been accomplished. The key features of the synthesis involve the highly stereoselective construction of the cis-trisubstituted cyclopentane intermediate by a Pd(0)-catalyzed cyclization, the stereospecific introduction of an angular hydroxyl group by Riley oxidation, and the efficient construction of the tricyclic system of (-)-galiellalactone via a combination of diastereoselective Hosomi-Sakurai crotylation and ring-closing metathesis (RCM). PMID:26544529

  18. Power Spectra of a Totally Asymmetric Simple Exclusion Process with Finite Resources

    Science.gov (United States)

    Cook, L. Jonathan; Zia, Royce K. P.

    2010-03-01

    In a cell, a mRNA has only a finite number of ribosomes to use during protein synthesis. We take this constraint into account in the modeling of translation by a totally asymmetric simple exclusion process (TASEP). Through Monte Carlo simulations and analytical methods, we study the power spectrum of the total particle occupancy of the TASEP. New features are found, such as a severe suppression at low frequencies. We formulate a theory based on a linearized Langevin equation with discrete space and time. With good agreement between the theoretical approach and the simulations, we gain some insight in how finite resources affect a TASEP.

  19. Inhomogeneous Generalization of a Multispecies Totally Asymmetric Zero Range Process

    Science.gov (United States)

    Kuniba, Atsuo; Maruyama, Shouya; Okado, Masato

    2016-06-01

    The n-species totally asymmetric zero range process (n-TAZRP) on a one-dimensional periodic chain studied recently by the authors is a continuous time Markov process where arbitrary number of particles can occupy the same sites and hop to the adjacent sites only in one direction with a priority constraint according to their species. In this paper we introduce an n-parameter generalization of the n-TAZRP having inhomogeneous transition rate. The steady state probability is obtained in a matrix product form and also by an algorithm related to combinatorial R.

  20. First total synthesis of Boehmenan

    Indian Academy of Sciences (India)

    Yamu Xia; Xiaoli Dai; Haixin Liu; Chen Chai

    2014-05-01

    The first total synthesis of dilignan Boehmenan has been achieved. A biomimetic oxidative coupling of the ferulic acid methyl ester in the presence of silver oxide is the crucial step in the synthesis sequence, generating the dihydrobenzofuran skeleton. Hydroxyl group was protected with DHP and reducted with LiAlH4 to afford the intermediate diol. The diol was condensated with the derivative of ferulic acid, then removed the protecting groups, to get Boehmenan. Meanwhile, a study on the ring-opening reaction of the intermediate dihydrobenzofuran neolignan under base conditions was described.

  1. Absolute Asymmetric Synthesis: The Origin, Control, and Amplification of Chirality

    OpenAIRE

    Delden, Richard A. van; Feringa, Bernard

    1999-01-01

    One of the fundamental and intriguing aspects of life is the homochirality of the essential molecules. From the early days of stereochemistry, the origin of chirality in biological systems has been a challenge to the chemical sciences and numerous theories and experiments have been reported. Despite the great progress in asymmetric synthesis, there are only a few genuine absolute asymmetric syntheses known today. Novel approaches based on the interplay of molecular biology, organic chemistry,...

  2. Catalytic asymmetric synthesis of phthioceranic acid, a heptamethyl-branched acid from Mycobacterium tuberculosis

    NARCIS (Netherlands)

    ter Horst, B.; Feringa, B.L.; J. Minnaard, A.

    2007-01-01

    The first total synthesis of phthioceranic acid (1) has been achieved by an iterative catalytic asymmetric 1,4-addition protocol. This method provides a robust and high-yielding route for the preparation of 1,3-oligomethyl (deoxypropionate) arrays. After the desired number of methyl groups has been

  3. Special Issue of "Asymmetric Synthesis"%Special Issue of "Asymmetric Synthesis"

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    Organic chemistry exploring the world at a molecu- lar level remains essential for our society in the 21st century. Asymmetric synthesis, particularly those em- ploying catalytic approach, is one of the most important research fields in organic synthesis providing chiral compounds in an enantiopure form. The latter is critical since the two enantiomers of one chiral compound, in many cases, have a different response in biological sys- tems. The huge markets of non-racemic chiral com- pounds as synthetic intermediates, pharmaceuticals,

  4. The Total Synthesis of Inostamycin A.

    Science.gov (United States)

    Yu, Guangri; Jung, Byunghyuck; Lee, Hee-Seung; Kang, Sung Ho

    2016-02-12

    The first total synthesis of inostamycin A is described. With efficient and stereoselective synthetic routes to aldehyde 3 and ketone 4 developed through asymmetric aldol reactions, addition reactions and reduction, and with chiral building blocks, the two large fragments were coupled with remarkable anti stereoselectivity and efficiency by aldol condensation. The coupling reaction provided the complete carbon skeleton with all the requisite functional groups and stereogenic centers for inostamycin A. The two quaternary carbons at C20 and C16 of ketone 4 were elaborated in a highly stereocontrolled manner by addition reactions of the transmetallated 5 to ethyl ketone 6 and the transmetallated 7 to methyl ketone 8, respectively, in which the use of LaCl3 for transmetallation was critical for high coupling efficiency. PMID:26800259

  5. Stereoselective Total Synthesis of Mycalamides

    Institute of Scientific and Technical Information of China (English)

    Masahiro Toyota

    2005-01-01

    @@ 1Introduction Mycalamides A (1a) and B (1b) are potent antiviral compounds from a New Zealand sponge of the genus Mycale. Apart from their antitumor property, mycalamide A (1a) exhibits immunosuppressive action by blocking T-cell activation in mice and is significantly more potent than FK-506 and cyclosporine A. Because of their intriguing biological activity, unique structures and scarce supply of these natural products, mycalamides A (1a) and B (1b) have attracted considerable attention as target molecules for total synthesis, and total, formal, or partial syntheses of this family of compounds have been reported[1,2].

  6. A Catalytic, Asymmetric Formal Synthesis of (+)-Hamigeran B

    KAUST Repository

    Mukherjee, Herschel

    2011-03-04

    A concise asymmetric, formal synthesis of (+)-hamigeran B is reported. A Pd-catalyzed, decarboxylative allylic alkylation, employing a trifluoromethylated derivative of t-BuPHOX, is utilized as the enantioselective step to form the critical quaternary carbon center in excellent yield and enantioselectivity. The product is converted in three steps to a late-stage intermediate previously used in the synthesis of hamigeran B.

  7. Synthesis of the 1,3-oxathiolanes using asymmetrically oxiranes

    Institute of Scientific and Technical Information of China (English)

    Faramarz Rostami-Charati; Zinatossadat Hossaini; Bita Mohtat; Mehdi Shahraki; Mohammad R. Hosseini-Tabatabaei

    2011-01-01

    An efficient synthesis of 1,3-oxathiolane-2-imin derivatives is described via one-pot reaction between arylisothiocyanats, asymmetrically substituted oxiranes and catalytic amount of methanol. The mild reaction conditions and high yields of the products exhibit the good synthetic advantage of this method.

  8. New approaches in asymmetric synthesis using γ-alkoxybutenolides

    NARCIS (Netherlands)

    Lange, Ben de; Jansen, Johan F.G.A.; Jong, Johannes C. de; Lubben, Marcel; Faber, Wijnand; Schudde, Ebe P.; Feringa, Bernard

    1992-01-01

    The synthesis of a new class of auxiliary based chiral synthons, γ-alkoxy-2(5H)-furanones, is described. The multifunctional compounds enter a variety of asymmetric transformations leading to acyclic- and cyclic-products with up to four new stereogenic centers in a single operation with stereoselect

  9. Selective Homogeneous Catalysis in Asymmetric Synthesis

    DEFF Research Database (Denmark)

    Fristrup, Peter

    The subject of this thesis is selectivity in homogeneous asymmetric transition metalcatalyzed reactions. Four different reactions within organic chemistry have been studied by kinetic measurements, computational chemistry (modelling) or both of them in parallel. A Hammett study was performed....... A thorough computational study succeeded in explaining the observed results, although other significant results were also obtained during this study. Finally, an intramolecular reaction was studied computationally, and the rate increase observed under phase transfer catalysis conditions could be related...

  10. The total synthesis of (-)-nitidasin.

    Science.gov (United States)

    Hog, Daniel T; Huber, Florian M E; Mayer, Peter; Trauner, Dirk

    2014-08-01

    Nitidasin is a pentacyclic sesterterpenoid with a rare 5-8-6-5 carbon skeleton that was isolated from the Peruvian folk medicine "Hercampuri". It belongs to a small class of sesterterpenoids that feature an isopropyl trans-hydrindane moiety fused to a variety of other ring systems. As a first installment of our general approach toward these natural products, we report the total synthesis of the title compound. Our stereoselective, convergent route involves the addition of a complex alkenyl lithium compound to a trans-hydrindanone, followed by chemoselective epoxidation, ring-closing olefin metathesis, and redox adjustment.

  11. Traceless Synthesis of Asymmetrically Modified Bivalent Nucleosomes.

    Science.gov (United States)

    Lechner, Carolin C; Agashe, Ninad D; Fierz, Beat

    2016-02-18

    Nucleosomes carry extensive post-translational modifications (PTMs), which results in complex modification patterns that are involved in epigenetic signaling. Although two copies of each histone coexist in a nucleosome, they may not carry the same PTMs and are often differently modified (asymmetric). In bivalent domains, a chromatin signature prevalent in embryonic stem cells (ESCs), namely H3 methylated at lysine 4 (H3K4me3), coexists with H3K27me3 in asymmetric nucleosomes. We report a general, modular, and traceless method for producing asymmetrically modified nucleosomes. We further show that in bivalent nucleosomes, H3K4me3 inhibits the activity of the H3K27-specific lysine methyltransferase (KMT) polycomb repressive complex 2 (PRC2) solely on the same histone tail, whereas H3K27me3 stimulates PRC2 activity across tails, thereby partially overriding the H3K4me3-mediated repressive effect. To maintain bivalent domains in ESCs, PRC2 activity must thus be locally restricted or reversed.

  12. An efficient asymmetric synthesis of (-)-wodeshiol

    Indian Academy of Sciences (India)

    Soon Ho Lee; Jae-Chul Jung; Oee Sook Park

    2011-05-01

    An efficient synthesis of (-)-wodeshiol 1 is described. The key reactions include highly stereoselective aldol condensation of piperonal with the dianion of chiral oxazolidinone, subsequent intramolecular ring cyclization of the aldol product 8 and a diastereocontrolled oxygenation of dilactone 7 in good yield.

  13. Phase-transfer-catalysed asymmetric synthesis of tetrasubstituted allenes

    Science.gov (United States)

    Hashimoto, Takuya; Sakata, Kazuki; Tamakuni, Fumiko; Dutton, Mark J.; Maruoka, Keiji

    2013-03-01

    Allenes are molecules based on three carbons connected by two cumulated carbon-carbon double bonds. Given their axially chiral nature and unique reactivity, substituted allenes have a variety of applications in organic chemistry as key synthetic intermediates and directly as part of biologically active compounds. Although the demands for these motivated many endeavours to make axially chiral, substituted allenes by exercising asymmetric catalysis, the catalytic asymmetric synthesis of fully substituted ones (tetrasubstituted allenes) remained largely an unsolved issue. The fundamental obstacle to solving this conundrum is the lack of a simple synthetic transformation that provides tetrasubstituted allenes in the action of catalysis. We report herein a strategy to overcome this issue by the use of a phase-transfer-catalysed asymmetric functionalization of 1-alkylallene-1,3-dicarboxylates with N-arylsulfonyl imines and benzylic and allylic bromides.

  14. Asymmetric synthesis using chiral-encoded metal

    Science.gov (United States)

    Yutthalekha, Thittaya; Wattanakit, Chularat; Lapeyre, Veronique; Nokbin, Somkiat; Warakulwit, Chompunuch; Limtrakul, Jumras; Kuhn, Alexander

    2016-08-01

    The synthesis of chiral compounds is of crucial importance in many areas of society and science, including medicine, biology, chemistry, biotechnology and agriculture. Thus, there is a fundamental interest in developing new approaches for the selective production of enantiomers. Here we report the use of mesoporous metal structures with encoded geometric chiral information for inducing asymmetry in the electrochemical synthesis of mandelic acid as a model molecule. The chiral-encoded mesoporous metal, obtained by the electrochemical reduction of platinum salts in the presence of a liquid crystal phase and the chiral template molecule, perfectly retains the chiral information after removal of the template. Starting from a prochiral compound we demonstrate enantiomeric excess of the (R)-enantiomer when using (R)-imprinted electrodes and vice versa for the (S)-imprinted ones. Moreover, changing the amount of chiral cavities in the material allows tuning the enantioselectivity.

  15. Asymmetric synthesis using chiral-encoded metal.

    Science.gov (United States)

    Yutthalekha, Thittaya; Wattanakit, Chularat; Lapeyre, Veronique; Nokbin, Somkiat; Warakulwit, Chompunuch; Limtrakul, Jumras; Kuhn, Alexander

    2016-01-01

    The synthesis of chiral compounds is of crucial importance in many areas of society and science, including medicine, biology, chemistry, biotechnology and agriculture. Thus, there is a fundamental interest in developing new approaches for the selective production of enantiomers. Here we report the use of mesoporous metal structures with encoded geometric chiral information for inducing asymmetry in the electrochemical synthesis of mandelic acid as a model molecule. The chiral-encoded mesoporous metal, obtained by the electrochemical reduction of platinum salts in the presence of a liquid crystal phase and the chiral template molecule, perfectly retains the chiral information after removal of the template. Starting from a prochiral compound we demonstrate enantiomeric excess of the (R)-enantiomer when using (R)-imprinted electrodes and vice versa for the (S)-imprinted ones. Moreover, changing the amount of chiral cavities in the material allows tuning the enantioselectivity. PMID:27562028

  16. Recent Advances in Substrate-Controlled Asymmetric Induction Derived from Chiral Pool α-Amino Acids for Natural Product Synthesis.

    Science.gov (United States)

    Paek, Seung-Mann; Jeong, Myeonggyo; Jo, Jeyun; Heo, Yu Mi; Han, Young Taek; Yun, Hwayoung

    2016-07-21

    Chiral pool α-amino acids have been used as powerful tools for the total synthesis of structurally diverse natural products. Some common naturally occurring α-amino acids are readily available in both enantiomerically pure forms. The applications of the chiral pool in asymmetric synthesis can be categorized prudently as chiral sources, devices, and inducers. This review specifically examines recent advances in substrate-controlled asymmetric reactions induced by the chirality of α-amino acid templates in natural product synthesis research and related areas.

  17. Asymmetric Synthesis of (R)-and (S)-Moprolol

    Institute of Scientific and Technical Information of China (English)

    WANG Zhao-yang; WANG Yan; SUN Li-wen; ZHU Jin-tao

    2008-01-01

    A simple and effective procedure for the enantioselective synthesis of (R)-and (S)-moprolol was described.The key step was the asymmetric synthesis of enantiopure (R)-and (S)-guaifenesin,which were synthesized from enantioenriched (R)-3-chloro-1,2-propanediol and (S)-epichlorohydrin via kinetics of hydrolysis resolution of racemic epichlorohydrin by chiral Salen-CoIIII complex.The e.e.values of both the optical compounds were above 98%,and the chemical structures of the target compounds were confirmed by 1H NMR,13C NMR,IR,and MS.

  18. De Novo Synthesis of Furanose Sugars: Catalytic Asymmetric Synthesis of Apiose and Apiose-Containing Oligosaccharides.

    Science.gov (United States)

    Kim, Mijin; Kang, Soyeong; Rhee, Young Ho

    2016-08-01

    A de novo synthetic method towards apiose, a structurally unusual furanose, is reported. The key feature is sequential metal catalysis consisting of the palladium-catalyzed asymmetric intermolecular hydroalkoxylation of an alkoxyallene and subsequent ring-closing metathesis (RCM). This strategy enabled the efficient synthesis of various apiose-containing disaccharides and a unique convergent synthesis of trisaccharides. PMID:27381592

  19. Asymmetric Synthesis of Fluoroamines from Chiral Aziridines

    Energy Technology Data Exchange (ETDEWEB)

    Park, Hyeonjeong; Yoon, Dooha; Ha, Hyunjoon [Hankuk Univ. of Foreign Studies, Yongin (Korea, Republic of); Son, Se In; Lee, Won Koo [Sogang Univ., Seoul (Korea, Republic of)

    2014-03-15

    We described an efficient preparation of fluoroamines by the ring-opening reactions of chiral aziridines with Et{sub 3}N·3HF. At most cases both regioisomers were obtained from the ring openings at C2 and C3 positions depending on the substituents at C2 of the starting substrates.The fluorinated organic molecules have attracted great attentions from synthetic and medicinal chemists with wide use of various agrochemicals and pharmaceuticals. Their uniqueness is originated from its electronic characteristics and the small size without altering the molecular conformations of non-fluorinated compounds. The fluorine is the second most widely used atom in the commercial drugs following the amine. Thereby, the elaboration of fluoro-amines bearing two most widely used atoms in drugs is one of the most challenging problems in drug synthesis and its development.

  20. Recent Advances in Catalytic Asymmetric Synthesis

    Institute of Scientific and Technical Information of China (English)

    A. M. P. Koskinen

    2005-01-01

    @@ 1Introduction The rapid development in the genomics and proteomics research has brought about an unprecedented number of potential new drug targets, which translates into an ever-increasing need to rapidly assemble highly pure small molecules (Mr≤850) with an increased structural complexity ‘to identify a small molecule partner for every gene product'[1]. Simultaneously, our increasing awareness of environmental aspects of synthesis places a nearly orthogonal set of requirements for the kinds of syntheses admissible in the future which can be expressed as a rule of 6S' s: selectivity and speed of the syntheses; safety, stability and sustainability of the processes; and scatter of diversity of the attainable products will be the key factors guiding the search for new synthetic organic chemistry.

  1. Asymmetric organic/metal(oxide) hybrid nanoparticles: synthesis and applications.

    Science.gov (United States)

    He, Jie; Liu, Yijing; Hood, Taylor C; Zhang, Peng; Gong, Jinlong; Nie, Zhihong

    2013-06-21

    Asymmetric particles (APs) with broken centrosymmetry are of great interest, due to the asymmetric surface properties and diverse functionalities. In particular, organic/metal(oxide) APs naturally combine the significantly different and complementary properties of organic and inorganic species, leading to their unique applications in various fields. In this review article, we highlighted recent advances in the synthesis and applications of organic/metal(oxide) APs. This type of APs is grounded on chemical or physical interactions between metal(oxide) NPs and organic small molecular or polymeric ligands. The synthetic methodologies were summarized in three categories, including the selective surface modifications, phase separation of mixed ligands on the surface of metal(oxide) NPs, and direct synthesis of APs. We further discussed the unique applications of organic/metal(oxide) APs in self-assembly, sensors, catalysis, and biomedicine, as a result of the distinctions between asymmetrically distributed organic and inorganic components. Finally, challenges and future directions are discussed in an outlook section.

  2. Stereoselective Total Synthesis of (-)-Renieramycin T.

    Science.gov (United States)

    Yokoya, Masashi; Toyoshima, Ryoko; Suzuki, Toshihiro; Le, Vy H; Williams, Robert M; Saito, Naoki

    2016-05-20

    A stereoselective total synthesis of (-)-Renieramycin T (1t) from a key tetrahydroisoquinoline intermediate previously utilized in our formal total synthesis of Ecteinascidin 743 is described. The synthesis features a concise approach for construction of the pentacyclic framework using a Pictet-Spengler cyclization of bromo-substituted carbinolamine 17, which obviates the regioselectivity problem of the Pictet-Spengler cyclization. The results of cytotoxicity studies are also presented. PMID:27019081

  3. Total synthesis of solanoeclepin A

    Science.gov (United States)

    Tanino, Keiji; Takahashi, Motomasa; Tomata, Yoshihide; Tokura, Hiroshi; Uehara, Taketo; Narabu, Takashi; Miyashita, Masaaki

    2011-06-01

    Cyst nematodes are troublesome parasites that live on, and destroy, a range of important host vegetable plants. Damage caused by the potato cyst nematode has now been reported in over 50 countries. One approach to eliminating the problem is to stimulate early hatching of the nematodes, but key hatching stimuli are not naturally available in sufficient quantities to do so. Here, we report the first chemical synthesis of solanoeclepin A, the key hatch-stimulating substance for potato cyst nematode. The crucial steps in our synthesis are an intramolecular cyclization reaction for construction of the highly strained tricyclo[5.2.1.01,6]decane skeleton (DEF ring system) and an intramolecular Diels-Alder reaction of a furan derivative for the synthesis of the ABC carbon framework. The present synthesis has the potential to contribute to addressing one of the critical food issues of the twenty-first century.

  4. Asymmetric Synthesis of β, γ-β-Hydroxyl-γ-butyrolactones

    Institute of Scientific and Technical Information of China (English)

    WANG Jin-Xin; ZHANG Chao-Xin; LI Ying

    2003-01-01

    @@ Chiral β-hydroxyl-γ-butyrolactones have attracted substantial interest in recent years due to their presence inmany strongly active natural products having antitumor, fungicidal, anti-inflammatory activity, and their use as important precursors in natural product synthesis. [1] In the course of the total synthesis of the natural product Tuxpano lide ,[2] we found a concise and efficient strategy on the stereocontrolled synthesis of β-hydroxyl-γ-butyrolactonederivatives from cheap and achiral starting material.

  5. Asymmetric Synthesis Using Enzymes in Supercritical CO2

    Institute of Scientific and Technical Information of China (English)

    T. Matsuda

    2005-01-01

    @@ 1Introduction Great efforts have been extended to catalysis in supercritical CO2 (scCO2) since the early 1990's due to the environmental friendliness, high diffusivity, high solubilizing power, easiness of the product separation,etc.. A combined process of scCO2 and enzymatic catalyst system would be a promising synthetic tool to produce optically active compounds because the enzyme has advantages of being natural and having high enantioselectivity in nature. Here we report asymmetric synthesis using lipase and alcohol dehydrogenase in scCO2[1,2].

  6. One-Pot Synthesis of (S)-Baclofen via Aldol Condensation of Acetaldehyde with Diphenylprolinol Silyl Ether Mediated Asymmetric Michael Reaction as a Key Step.

    Science.gov (United States)

    Hayashi, Yujiro; Sakamoto, Daisuke; Okamura, Daichi

    2016-01-01

    An efficient asymmetric total synthesis of (S)-baclofen was accomplished via a one-pot operation from commercially available materials using sequential reactions, such as aldol condensation of acetaldehyde, diphenylprolinol silyl ether mediated asymmetric Michael reaction of nitromethane, Kraus-Pinnick oxidation, and Raney Ni reduction. Highly enantioenriched baclofen was obtained in one pot with a good yield over four reactions. PMID:26636719

  7. Asymmetric Synthesis of (-)-Incarvillateine Employing an Intramolecular Alkylation via Rh-Catalyzed Olefinic C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Tsai, Andy; Bergman, Robert; Ellman, Jonathan

    2008-02-18

    An asymmetric total synthesis of (-)-incarvillateine, a natural product having potent analgesic properties, has been achieved in 11 steps and 15.4% overall yield. The key step is a rhodium-catalyzed intramolecular alkylation of an olefinic C-H bond to set two stereocenters. Additionally, this transformation produces an exocyclic, tetrasubstituted alkene through which the bicyclic piperidine moiety can readily be accessed.

  8. Short synthesis of the C1-C14 stretch of discodermolide from building blocks prepared by asymmetric catalysis.

    Science.gov (United States)

    Cao, Huanyan; Parker, Kathlyn A

    2008-04-01

    A convergent and stereoselective synthesis of the C1-C14 stretch of (+)-discodermolide demonstrates the utility of the "asymmetric catalysis approach" to complex polypropionates. The preparation of this complex synthon requires 15 steps in the longest linear sequence and 19 steps total from inexpensive materials.

  9. Mo-catalyzed asymmetric olefin metathesis in target-oriented synthesis: Enantioselective synthesis of (+)-africanol

    Science.gov (United States)

    Weatherhead, Gabriel S.; Cortez, G. A.; Schrock, Richard R.; Hoveyda, Amir H.

    2004-01-01

    Catalytic asymmetric ring-opening metathesis (AROM) provides an efficient method for the synthesis of a variety of optically enriched small organic molecules that cannot be easily prepared by alternative methods. The development of Mo-catalyzed AROM transformations that occur in tandem with ring-closing metathesis are described. The utility of the Mo-catalyzed AROM/ring-closing metathesis is demonstrated through an enantioselective approach to the synthesis of (+)-africanol. PMID:15056762

  10. A modified total synthesis of cystothiazole A

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    A modified total synthesis of cystothiazole A is described. In this synthetic strategy, a one-step transformation of acylated oxazolidinone to β-ketoester has been successfully applied, thus making the synthetic route more efficient. This method may also be potentially applied in synthesis of other related β-substituted-β-methoxyl acrylates (bb-MOAs).

  11. Total Synthesis of (±)-Celaphanol A

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The first total synthesis of (±)-Celaphanol A was accomplished starting from α-cyclocitral and 3,4-dimethoxy benzyl chloride via a six-step process, in which the intramolecular cyclization of ketone 4 with BF3@Et2O afforded an all-cis isomer intermediate for synthesis of aromatic tricyclic diterpenes.

  12. Total Synthesis of (±)-Hibiscone C

    OpenAIRE

    Ungureanu, Sinziana; Meadows, Maggie; Smith, Joel; Duff, David B.; Burgess, James M.; Goess, Brian C.

    2011-01-01

    A total synthesis of (±)- hibiscone C, one member of the furanosteroid family of natural products that also includes viridin and wortmannin, is reported. Two new pathways for formation of the key diacyl furan subunit are described.

  13. The First Total Synthesis of Isoliquiritin

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A first total synthesis of isoliquiritin was accomplished starting from p-hydroxy- benzaldehyde and 2,4-dihydroxyacetylphenone. The key step is condensation reaction. In synthetic process need not protect the hydroxy group of reacting substance.

  14. Highly Efficient Asymmetric Synthesis Usomg Organocatalyst Derived From(S)-proline

    Institute of Scientific and Technical Information of China (English)

    T.Oriyama

    2007-01-01

    1 Results Much effort has been focused on organocatalytic asymmetric synthesis in these several years. We have already documented highly efficient organocatalytic asymmetric acylation of a wide variety of racemic alcohols and meso-diols catalyzed bya chiral 1,2-diamine derived from (S)-proline[1]. (S)-Homoproline seems to be a potentially interesting organocatalyst, but no examples using (S)-homoproline itself in asymmetric synthesis has been reported. We have accomplished an efficient and practical syn...

  15. Synthesis of 7,7'-Disubstituted BINAP and Their Application in Asymmetric Catalytic Reaction

    Institute of Scientific and Technical Information of China (English)

    Yuan Wei-Cheng; Liu Hua; Mi Ai-Qiao; Gong Liu-Zhu; Jiang Yao-Zhong

    2004-01-01

    The design of new chiral ligands plays a very important role in the development of transition metal catalyzed asymmetric synthesis. Many chiral diphosphine ligands have been prepared and applied in asymmetric catalytic reactions with excellent enantioselectivities. Among the chiral diphosphine ligands reported, BINAP was found to have been the widest application in the transition metal catalyzed reaction. Recently we have developed a novel oxovanadium (Ⅳ)complex catalyst for the oxidative coupling of naphthol with high enantioselectivity.[1] And then a series of optically pure 7,7'-disubstituted BINOLs were successfully synthesized by using the catalyst,[2] on the basis of above, the 7,7'-disubstituted BINAP ligands ( 1-5 ) were easily prepared from the 7,7'-disubstituted BINOLs with high total yields (up to 64% of 5 steps from the BINOLs ).To demonstrate the efficiency of ligands 1-5, we applied their ruthenium complexes for asymmetric hydrogenation of simple ketones with high activity (S/C up to 5000 ), high converation (up to 100%) and moderate enantioselectivity (ee up to 88.3% ) under mild conditions. In addition, in the asymmetric 1,4-addition of arylboronic acids, these ligands also provide excellent enantioselectivity (ee up to 99%) and yield ( up to 99%).

  16. Calculation of Total Cost, Tolerance Based on Taguchi’s, Asymmetric Quality Loss Function Approach

    Directory of Open Access Journals (Sweden)

    R. S. Kumar

    2009-01-01

    Full Text Available Problem statement: Current world market force the manufacturing sectors to develop high quality product and process design with minimum possible cost. About 80% of problems in production units may be attributed to 20% of design tolerance causes. While design typically represents the smallest actual cost elements in products (around 5%, it leverages the largest cost influence (around 70%. So design engineers continuously stumble upon problem of design for high quality performance with lower cost. Objectives of this study where to: (i simultaneous selection of design and manufacturing tolerance (ii minimization of total cost (sum of the manufacturing cost and Taguchi’s asymmetric quality cost (iii minimum cost and its machining tolerance. Approach: Rotor key base assembly was considered as case study to optimize the minimization of assembly total cost and machining tolerance. New global nonlinear optimization techniques called pattern search algorithm had been implemented to find optimal tolerance allocation and total cost. Results: In this study minimum cost arrived was 45.15 Cr and its corresponding tolerances for machining process turning, drilling, face milling, face milling and drilling where 0.063, 0.0508, 0.2127, 0.2127, 0.2540 mm respectively at worst case conditions. Conclusion: Results indicated that optimization by integer programming, sequential quadratic programming and exhaustive search, nonlinear programming, genetic algorithm, simulated annealing, fuzzy logic, number set theory and Monte Carlo simulation did not give much least total cost and also predicted that pattern search algorithm was robust method. Second the method, generally termed as concurrent tolerance synthesis was well suited for engineering environment, where high quality products with low total cost were designed and manufactured.

  17. A Biomimetic Strategy to Access the Silybins: Total Synthesis of (−)-Isosilybin A

    OpenAIRE

    McDonald, Benjamin R.; Nibbs, Antoinette E.; Scheidt, Karl A.

    2014-01-01

    We report the first asymmetric, total synthesis of (−)-isosilybin A. A late-stage catalytic biomimetic cyclization of a highly functionalized chalcone is employed to form the characteristic benzopyranone ring. A robust and flexible approach to this chalcone provides an entry to the preparation of the entire isomeric family of silybin natural products.

  18. Total Synthesis of balanol, Part 2

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Kelly, Nicholas; Tedenborg, Lars;

    1997-01-01

    A convergent enantioselective total synthesis of the natural product (-)-balanol (1) is described. In addition to benzophenone fragment 8, key intermediates are chiral bicyclic aziridine 3 and the corresponding epoxide 4, both of which undergo highly regio- and stereoselective nucleophilic ring-o...

  19. Enantioselective Total Synthesis of Plectosphaeroic Acid B

    OpenAIRE

    Jabri, Salman Y.; Overman, Larry E.

    2013-01-01

    The first total synthesis of a member of the plectosphaeroic acid family of fungal natural products is reported. Key steps include the late-stage formation of the hindered N6–C9″ bond and stereoselective introduction of the two methylthio substituents.

  20. The total synthesis of (-)-cryptocaryol A.

    Science.gov (United States)

    Dias, L C; Kuroishi, P K; de Lucca, E C

    2015-03-28

    A stereoselective total synthesis of (-)-cryptocaryol A (1) is described. Key features of the 17-step route include the use of three boron-mediated aldol reaction-reduction sequences to control all stereocenters and an Ando modification of the Horner-Wadsworth-Emmons olefination that permitted the installation of the Z double bond of the α-pyrone ring. PMID:25695350

  1. The total synthesis of pantocin B.

    Science.gov (United States)

    Sutton, A E; Clardy, J

    2000-02-10

    [reaction: see text] Pantocin B, an unusual antibiotic produced by Erwinia herbicola, effectively controls E. amylovora, the pathogen causing the plant disease fire blight. A total synthesis of pantocin B from L-alanine, glycine, and L-malic acid is reported. PMID:10814312

  2. Total synthesis of insect antifeedant drimane sesquiterpenes.

    NARCIS (Netherlands)

    Jansen, B.J.M.

    1993-01-01

    The investigations described in this thesis deal with the total synthesis of sesquiterpenes of the drimane family, named for their widespread occurrence in the stem bark of South American Drimys species. These compounds contain the bicyclofarnesol nucleus 1 , which is invariably oxi

  3. Stereocontrolled total synthesis of hedyotol A.

    Science.gov (United States)

    Kawabe, Yusuke; Ishikawa, Ryo; Akao, Yusuke; Yoshida, Atsushi; Inai, Makoto; Asakawa, Tomohiro; Hamashima, Yoshitaka; Kan, Toshiyuki

    2014-04-01

    The total synthesis of hedyotol A (1), a natural product isolated from Hedyotis lawsoniae (DC.) Wight et Arn. (Rubiaceae), was accomplished in a highly stereocontrolled manner. Key steps include an L-proline-catalyzed cross-aldol reaction and the biomimetic construction of a furofuran lignan skeleton through a quinomethide intermediate. PMID:24660822

  4. Study Toward the Total Synthesis of Pyrenophorin

    Directory of Open Access Journals (Sweden)

    Everaldo F. Santos Filho

    2012-06-01

    Full Text Available Macrodiolides are macrocyclic compounds containing two ester groups in a cyclic chain. Of this class of compounds, Pyrenophorin (1 shows antifungal activity, and is produced from the pathogenic fungus Pyrenophora avenae. As this substance, derived from nature, is isolated in small quantities, an asymmetric synthesis using a simple and efficient methodology would be of great interest. The proposed synthetic route starts with the protection of propargyl alcohol 3 using DHP and feldspar as catalyst. Compound 5 obtained in this reaction was then subjected to acid-base reaction between the acetylenic proton and 1 eq. n-BuLi, leading to formation of the acetylide 5A. The 1,2- addition reaction between 5A and g-valerolactone (6 leads to the formation of alkinone 7 in 67% yield. Subsequently, compound 7 was subjected to a ketalization reaction using the same feldspar catalyst. Ketal 8 was formed under concomitant removal of the THP group. The product of this reaction (8 was then submitted to a reduction reaction of the triple bond to form olefin 9 with E configuration. Currently, the conditions for obtaining 10 by oxidation using Jones reagent, are being optimized. Compound 10,    obtained as described, is being subjected to a macrolactonization reaction. Various conditions including the use of enzymes are being studied. In addition, a study involving the enantioselective synthesis of (R,R-(--pyrenophorin, using enzymatic kinetic resolution of the racemic mixture of compound 8, is in progress in the group

  5. Asymmetric synthesis of cyclo-archaeol and ß-glucosyl cyclo-archaeol

    NARCIS (Netherlands)

    Ferrer, C.; Fodran, P.; Barroso, S.; Gibson, R.; Hopmans, E.C.; Sinninghe Damsté, J.S.; Schouten, S.; Minnaard, A.J.

    2013-01-01

    An efficient asymmetric synthesis of cyclo-archaeol and beta-glucosyl cyclo-archaeol is presented employing catalytic asymmetric conjugate addition and catalytic epoxide ring opening as the key steps. Their occurrence in deep sea hydrothermal vents has been confirmed by chromatographic comparison wi

  6. Asymmetric synthesis of cyclo-archaeol and beta-glucosyl cyclo-archaeol

    NARCIS (Netherlands)

    Ferrer, Catalina; Fodran, Peter; Barroso, Santiago; Gibson, Robert; Hopmans, Ellen C.; Damste, Jaap Sinninghe; Schouten, Stefan; Minnaard, Adriaan J.

    2013-01-01

    An efficient asymmetric synthesis of cyclo-archaeol and beta-glucosyl cyclo-archaeol is presented employing catalytic asymmetric conjugate addition and catalytic epoxide ring opening as the key steps. Their occurrence in deep sea hydrothermal vents has been confirmed by chromatographic comparison wi

  7. First Total Synthesis of Gliomasolide C and Formal Total Synthesis of Sch-725674.

    Science.gov (United States)

    Seetharamsingh, B; Khairnar, Pankaj V; Reddy, D Srinivasa

    2016-01-01

    Syntheses of two 14-membered macrolides Sch-725674 and Gliomasolide C are described here. The first total synthesis of Gliomasolide C, the short synthesis of Sch-725674, and regioselective Wacker oxidation of internal olefin are the highlights of this disclosure. In addition, a key macrocycle with orthogonal functionalities was designed and synthesized on a gram scale for the generation of analogues. PMID:26633579

  8. Shocks induced by junctions in totally asymmetric simple exclusion processes under periodic boundary condition

    Science.gov (United States)

    Sun, Xiaoyan; Xie, Yanbo; He, Zhiwei; Wang, Binghong

    2011-07-01

    This Letter investigates a totally asymmetric simple exclusion process (TASEP) with junctions in a one-dimensional transport system. Parallel update rules and periodic boundary condition are adopted. Two cases corresponding to different update rules are studied. The results show that the stationary states of system mainly depend on the selection behavior of particle at the bifurcation point.

  9. Nineteen-step total synthesis of (+)-phorbol.

    Science.gov (United States)

    Kawamura, Shuhei; Chu, Hang; Felding, Jakob; Baran, Phil S

    2016-04-01

    Phorbol, the flagship member of the tigliane diterpene family, has been known for over 80 years and has attracted attention from many chemists and biologists owing to its intriguing chemical structure and the medicinal potential of phorbol esters. Access to useful quantities of phorbol and related analogues has relied on isolation from natural sources and semisynthesis. Despite efforts spanning 40 years, chemical synthesis has been unable to compete with these strategies, owing to its complexity and unusual placement of oxygen atoms. Purely synthetic enantiopure phorbol has remained elusive, and biological synthesis has not led to even the simplest members of this terpene family. Recently, the chemical syntheses of eudesmanes, germacrenes, taxanes and ingenanes have all benefited from a strategy inspired by the logic of two-phase terpene biosynthesis in which powerful C-C bond constructions and C-H bond oxidations go hand in hand. Here we implement a two-phase terpene synthesis strategy to achieve enantiospecific total synthesis of (+)-phorbol in only 19 steps from the abundant monoterpene (+)-3-carene. The purpose of this synthesis route is not to displace isolation or semisynthesis as a means of generating the natural product per se, but rather to enable access to analogues containing unique placements of oxygen atoms that are otherwise inaccessible. PMID:27007853

  10. Total Synthesis of (±)-Integrifolin.

    Science.gov (United States)

    Shimomaki, Katsuya; Kusama, Hiroyuki; Iwasawa, Nobuharu

    2016-07-11

    The total synthesis of (±)-integrifolin has been achieved for the first time through the stereoselective preparation of the bicyclo[5.3.0]decane skeleton based on the tungsten-catalyzed cyclization of acyclic trienynes under photoirradiation conditions. Further key transformations of the cyclized product are the Tamao oxidation through cyclic silyl ether, the introduction of two oxygen functionalities by the oxidation of the diene and the construction of three exo-methylene moieties. PMID:27147582

  11. Synthesis of the tetracyclic core of Illicium sesquiterpenes using an organocatalyzed asymmetric Robinson annulation

    OpenAIRE

    Trzoss, Lynnie; Xu, Jing; Lacoske, Michelle H.; Theodorakis, Emmanuel A.

    2013-01-01

    An enantioselective synthesis of the core framework of neurotrophic Illicium majucin-type sesquiterpenes is described here. This strategy is based on an organocatalyzed asymmetric Robinson annulation and provides an efficient approach for a diversity-oriented synthesis of Illicium natural products that holds remarkable therapeutic potential for neurodegenerative diseases.

  12. Total synthesis and biological investigation of (-)-promysalin.

    Science.gov (United States)

    Steele, Andrew D; Knouse, Kyle W; Keohane, Colleen E; Wuest, William M

    2015-06-17

    Compounds that specifically target pathogenic bacteria are greatly needed, and identifying the method by which they act would provide new avenues of treatment. Herein we report the concise, high-yielding total synthesis (eight steps, 35% yield) of promysalin, a natural product that displays antivirulence phenotypes against pathogenic bacteria. Guided by bioinformatics, four diastereomers were synthesized, and the relative and absolute stereochemistries were confirmed by spectral and biological analysis. Finally, we show for the first time that promysalin displays two antivirulence phenotypes: the dispersion of mature biofilms and the inhibition of pyoverdine production, hinting at a unique pathogenic-specific mechanism of action.

  13. Total synthesis of insect antifeedant drimane sesquiterpenes.

    OpenAIRE

    Jansen, B.J.M.

    1993-01-01

    The investigations described in this thesis deal with the total synthesis of sesquiterpenes of the drimane family, named for their widespread occurrence in the stem bark of South American Drimys species. These compounds contain the bicyclofarnesol nucleus 1 , which is invariably oxidized at C-11 and/or C-12 and often at other sites as well (see figure 8.1).A few rearranged drimanes, e.g., (+)-colorata-4(13),8-dienolide 6 , and (-)-muzigadial 7 , are also isolated from natural products. The re...

  14. Enantioconvergent synthesis by sequential asymmetric Horner-Wadsworth-Emmons and palladium-catalyzed allylic substitution reactions

    DEFF Research Database (Denmark)

    Pedersen, Torben Møller; Hansen, E. Louise; Kane, John;

    2001-01-01

    A new method for enantioconvergent synthesis has been developed. The strategy relies on the combination of an asymmetric Horner-Wadsworth-Emmons (HWE) reaction and a palladium-catalyzed allylic substitution. Different $alpha@-oxygen-substituted, racemic aldehydes were initially transformed by...... asymmetric HWE reactions into mixtures of two major $alpha@,$beta@-unsaturated esters, possessing opposite configurations at their allylic stereocenters as well as opposite alkene geometry. Subsequently, these isomeric mixtures of alkenes could be subjected to palladium-catalyzed allylic substitution...

  15. First total synthesis of 10α-hydroxy-4-muurolen-3-one and its C10-isomer

    Institute of Scientific and Technical Information of China (English)

    Fu Qiang Bi; Li Jing Fang; Chen Xi Zhang; Yu Lin Li

    2008-01-01

    An efficient synthetic route to muurolane type sesquiterpenes starting from (R)-carvone,employing allylic diazene rearrange-ment and the ring closing methesis (RCM) reaction as key steps,is described.The first asymmetric total synthesis of (-)-10α-hydroxy-4-muurolen-3-one B and (-)-10β-hydroxy-4-muurolen-3-one C was accomplished.Through the total synthesis,the absolute configurations of the natural products A,B and C were established.

  16. Enantioselective Total Synthesis of (-)-Alstoscholarisine A.

    Science.gov (United States)

    Liang, Xiao; Jiang, Shi-Zhi; Wei, Kun; Yang, Yu-Rong

    2016-03-01

    We report a concise and highly enantioselective total synthesis of (-)-alstoscholarisine A (1), a recently isolated monoterpenoid indole alkaloid that has significant bioactivity in promoting adult neuronal stem cells proliferation. A highly enantioselective (99% ee), intramolecular Ir-catalyzed Friedel-Crafts alkylation of indole 9 with a secondary allylic alcohol was utilized to establish the first stereogenic center upon which the other three contiguous chiral centers were readily set by a highly stereoselective tandem 1,4-addition and aldol reaction. The key tetrahydropyran was constructed through a hemiacetal reduction, and the final aminal bridge was forged by a one-pot reductive amination/cyclization. The conciseness of this approach was highlighted by building core bonds in each step with a minimalist protecting group strategy. PMID:26882407

  17. Total synthesis of diterpenoid steenkrotin A.

    Science.gov (United States)

    Pan, Saiyong; Xuan, Jun; Gao, Beiling; Zhu, An; Ding, Hanfeng

    2015-06-01

    A concise and diastereoselective total synthesis of the diterpenoid (±)-steenkrotin A is described for the first time. The strategy mainly features three key ring formations: 1) a rhodium-catalyzed O-H bond insertion followed by an intramolecular carbonyl-ene reaction to build up the tetrahydrofuran subunit; 2) sequential SmI2 -mediated Ueno-Stork and ketyl-olefin cyclizations to construct the [5,7] spirobicyclic skeleton; and 3) an intramolecular aldol condensation/vinylogous retro-aldol/aldol sequence to form the final six-membered ring with inversion of the relative configuration at the C7 position. PMID:25891977

  18. A Pot-Economical Approach to the Total Synthesis of Sch-725674.

    Science.gov (United States)

    Bodugam, Mahipal; Javed, Salim; Ganguly, Arghya; Torres, Jessica; Hanson, Paul R

    2016-02-01

    A pot-economical total synthesis of antifungal Sch-725674, 1, is reported. The approach takes advantage of a number of one-pot, sequential transformations, including a phosphate tether-mediated one-pot, sequential RCM/CM/chemoselective hydrogenation protocol, a one-pot tosylation/acrylation sequence, and a one-pot, sequential Finkelstein reaction/Boord olefination/acetonide deprotection procedure to streamline the synthesis route by reducing isolation and purification procedures, thus saving time. Overall, an asymmetric route has been developed that is efficiently accomplished in seven pots from phosphate (S,S)-triene and with minimal purification. PMID:26760683

  19. Asymmetric Imine Isomerisation in the Enantioselective Synthesis of Chiral Amines from Prochiral Ketones

    NARCIS (Netherlands)

    Willems, Johannes G.H.; Vries, Johannes G. de; Nolte, Roeland J.M.; Zwanenburg, Binne

    1995-01-01

    An asymmetric catalytic synthesis of chiral amines using a chiral base catalysed [1,3]-proton shift reaction of imines is described. The isomerisation reaction of N-benzylimines derived from prochiral ketones (benzylacetone, acetophenone) and p-substituted benzylamines, is catalysed by chiral alcoho

  20. A Convenient Method to Construct Chroman Skeleton: Asymmetric Synthesis of (-)-4'-Hydroxy-7-methoxyflavane

    Institute of Scientific and Technical Information of China (English)

    XU, Boyan; XUE, Jijun; ZHANG, Huabing; LI, Ying

    2009-01-01

    The first enantioselective synthesis of a naturally occurring 4'-hydroxy-7-methoxyflavane was developed by an asymmetric reduction and a microwave-assistant aromatic C-O bond formation to construct the benzopyran skele- ton. Key features of this method include its brevity, its preserved stereochemical integrity and two different syn- thetic routes to choose.

  1. Organocatalytic One-Pot Asymmetric Synthesis of Thiolated Spiro-γ-lactam Oxindoles Bearing Three Stereocenters.

    Science.gov (United States)

    Huang, Xin; Liu, Miao; Pham, Kenny; Zhang, Xiaofeng; Yi, Wen-Bin; Jasinski, Jerry P; Zhang, Wei

    2016-07-01

    The first asymmetric synthesis of spiro-γ-lactam oxindoles bearing three stereocenters is reported. One-pot thiol-Michael/Mannich/lactamization reactions promoted by a recyclable fluorous bifunctional cinchona alkaloid/thiourea organocatalyst afford products in moderate to good yields with up to 95% ee and 6:1 dr. PMID:27258150

  2. Fructose derived pyridyl alcohol ligands: synthesis and application in the asymmetric diethylzinc addition to aldehydes

    Institute of Scientific and Technical Information of China (English)

    ZHOU, Yong-Gui; DAI, Li-Xin; HOU, Xue-Long

    2000-01-01

    Easily available chiral ketones were employed for the synthesis of optically active pyridyl alcohols, which were applied in the asymmetric diethylzinc addition to aldehydes, up to 89.4%e.e. was obtained using D-fructose-derived pyridyl alcohol.

  3. Recent advances in the catalytic asymmetric synthesis of β-amino acids

    NARCIS (Netherlands)

    Weiner, Barbara; Szymanski, Wiktor; Janssen, Dick B.; Minnaard, Adriaan J.; Feringa, Ben L.

    2010-01-01

    In this critical review, the progress in catalytic asymmetric synthesis of β-amino acids is discussed, covering the literature since 2002. The review treats transition metal catalysis, organocatalysis and biocatalysis and covers the most important synthetic methods, such as hydrogenation, the Mannic

  4. Amitorines A and B, Nitrogenous Diterpene Metabolites of Theonella swinhoei: Isolation, Structure Elucidation, and Asymmetric Synthesis.

    Science.gov (United States)

    Ota, Koichiro; Hamamoto, Yukiko; Eda, Wakiko; Tamura, Kenta; Sawada, Akiyoshi; Hoshino, Ayako; Mitome, Hidemichi; Kamaike, Kazuo; Miyaoka, Hiroaki

    2016-04-22

    Two new nitrogenous prenylbisabolanes never before found in Lithistid sponges have been isolated from Theonella swinhoei. These new diterpenes, named amitorine A (1) and amitorine B (2), containing a prenylbisabolane skeleton have been characterized by spectroscopic analyses, and the relative and absolute configurations of 1 and 2 were determined by asymmetric synthesis of both diastereomers via the common bicyclic lactone 6 intermediate.

  5. Determinantal Representation of the Time-Dependent Stationary Correlation Function for the Totally Asymmetric Simple Exclusion Model

    Directory of Open Access Journals (Sweden)

    Nikolay M. Bogoliubov

    2009-04-01

    Full Text Available The basic model of the non-equilibrium low dimensional physics the so-called totally asymmetric exclusion process is related to the 'crystalline limit' (q → ∞ of the SU_q(2 quantum algebra. Using the quantum inverse scattering method we obtain the exact expression for the time-dependent stationary correlation function of the totally asymmetric simple exclusion process on a one dimensional lattice with the periodic boundary conditions.

  6. Synthesis of antidepressant duloxetine via asymmetric transfer hydrogenation

    Institute of Scientific and Technical Information of China (English)

    Shan Zhen He; Xue Ming Li; Jia Dai; Ming Yan

    2008-01-01

    Antidepressant duloxetine (1) was prepared via asymmetric transfer hydrogenation of 3-(dimethylamino)-1-(thiophen-2-yl)propan-1-one (3). The Ru(Ⅱ), Rh(Ⅲ) and Ir(Ⅲ) complexes of several chiral ligands were examined as the catalyst and(S,S)-N-tosyl-1,2-diphenyl ethylenediamine (TsDPEN)-Ru(Ⅱ) complex was found to provide good yield and excellent enantios-electivity.

  7. Asymmetric synthesis of polypiperylene on a lanthanide-containing catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Monakov, Yu.B.; Marina, N.G.; Kozlova, O.I.; Kanzafarov, F.Ya.; Tolstikov, G.A.

    1987-07-01

    The authors study the polymerization of piperylene and subsequent synthesis of polypiperylene on a neodymium chloride catalyst containing a sulfoxide and an aluminium complex. Specifics of the catalyst preparation and activity are given.

  8. Synthesis of New Chiral Phosphine Ligands and Their Application in Asymmetric Hydrogenation of Ketones

    Institute of Scientific and Technical Information of China (English)

    XIE Jian-Hua; FU Yu; WANG Li-Xin; ZHOU Qi-Lin

    2004-01-01

    The design of new chiral ligands is the key in the development of transition metal catalyzed asymmetric synthesis. Many chiral diphosphine ligands have been prepared and applied in asymmetric catalytic reactions with excellent enantioselectivities. Among the chiral diphosphine ligands that have been reported, the atropisomeric C2-symmetric phosphines with a biaryl scaffold initiated by Noyori and co-workers with BINAP were found to have the widest application in the transition metal catalyzed reactions. Planar chiral diphosphines based on ferrocene or paracyclophane backbones have also been applied to a number of reactions with a remarkable degree of success. However, the spiro diphosphine compounds, another type of axially chiral ligands, have not been synthesized yet. Recently, we designed chiral phosphoramidite ligands (SIPHOS)containing a 1, 1′-spirobiindane backbone and demonstrated that these ligands can be highly efficient for the Rh-catalyzed asymmetric hydrogenation of functionalized olefins. Especially, in the case of asymmetric hydrogenation of α-arylethenylamines, the spiro monophosphoramidite ligands provided a significantly higher level of enantiocontrol compared to that of the monophosphoramidite ligands derived from BINOL. Herein we present the synthesis of spiro diphosphines (SDP) containing 1,1′-spirobiindane as a new chiral scaffold and their application in the ruthenium-catalyzed asymmetric hydrogenation of simple ketones with high activity (S/C up to 100 000) and excellent enantioselectivity (ee up to 99.5%).

  9. Total Synthesis of a Diacetonide Derivative of Thuggacin A.

    Science.gov (United States)

    Yadav, Jhillu S; Dutta, Palash

    2016-03-01

    A highly stereoselective total synthesis of the diacetonide derivative of the antibiotic thuggacin A has been described. The synthesis features the stereoselective Stille cross-coupling reaction to set up the whole carbon framework, aldol condensation to construct the highly substituted conjugated diene, non-Evans syn aldol, CBS reduction, Hantzsch's thiazole synthesis, Horner-Wadsworth-Emmons reaction, and Shiina's macrolactonization. PMID:26856208

  10. Total Synthesis of the Cyanolide A Aglycon

    OpenAIRE

    Gesinski, Michael R.; Rychnovsky, Scott D.

    2011-01-01

    The synthesis of the potent molluscicide, cyanolide A, has been achieved in 10 steps without the use of protecting groups. The synthesis features a key Sakurai macrocyclization/dimerization reaction that simultaneously forms both tetrahydropyran rings and the macrocycle of the natural product.

  11. The total synthesis of cannabisin G

    Directory of Open Access Journals (Sweden)

    YAMU XIA

    2010-12-01

    Full Text Available A convenient method for the synthesis of lignanamide cannabisin G, starting from vanillin, was developed. The convergent synthesis was based on the Stobbe reaction as C–C bond-forming steps to give the skeleton of lignan, which was condensed with a derivative of tyramine to obtain synthetic cannabisin G for the first time.

  12. Direct Asymmetric Aldol Type Reaction with Ethyl Diazoacetate: Stereoselective Synthesis of α, β-Dihydroxy Esters

    Institute of Scientific and Technical Information of China (English)

    LIAO Ming-Yi; YAO Wen-Gang; FENG Hai-Tao; WANG Jian-Bo

    2003-01-01

    @@ Enantioselective aldol condensation under catalytic condition remains a challenging task in modern organic synthesis, and numerous efforts have been directed to this area. In particular, the direct catalytic asymmetric aldol reaction is very attractive considering the requirement of atom efficiency. This has been studied only recently, and several very practical processes have been developed. We have recently initiated a study on the direct asymmetric aldol type reaction with ethyl diazoacetate as nucleophile. Moderate enantioselectivities (65% ~91% ee ) were achieved in the condensation of aldehydes with ethyl diazoacetate catalyzed by the chiral complex of BINOL derivatives-Zr (OBu- t )4. [1

  13. Large-scale asymmetric synthesis of a cathepsin S inhibitor.

    Science.gov (United States)

    Lorenz, Jon C; Busacca, Carl A; Feng, XuWu; Grinberg, Nelu; Haddad, Nizar; Johnson, Joe; Kapadia, Suresh; Lee, Heewon; Saha, Anjan; Sarvestani, Max; Spinelli, Earl M; Varsolona, Rich; Wei, Xudong; Zeng, Xingzhong; Senanayake, Chris H

    2010-02-19

    A potent reversible inhibitor of the cysteine protease cathepsin-S was prepared on large scale using a convergent synthetic route, free of chromatography and cryogenics. Late-stage peptide coupling of a chiral urea acid fragment with a functionalized aminonitrile was employed to prepare the target, using 2-hydroxypyridine as a robust, nonexplosive replacement for HOBT. The two key intermediates were prepared using a modified Strecker reaction for the aminonitrile and a phosphonation-olefination-rhodium-catalyzed asymmetric hydrogenation sequence for the urea. A palladium-catalyzed vinyl transfer coupled with a Claisen reaction was used to produce the aldehyde required for the side chain. Key scale up issues, safety calorimetry, and optimization of all steps for multikilogram production are discussed. PMID:20102230

  14. Time-headway distribution for periodic totally asymmetric exclusion process with various updates

    Science.gov (United States)

    Hrabák, P.; Krbálek, M.

    2016-03-01

    The totally asymmetric exclusion process (TASEP) with periodic boundaries is considered as traffic flow model. The large-L approximation of the stationary state is used for the derivation of the time-headway distribution (an important microscopic characteristic of traffic flow) for the model with generalized update (genTASEP) in both, forward- and backward-sequential representations. The usually used updates, fully-parallel and regular forward- and backward-sequential, are analyzed as special cases of the genTASEP. It is shown that only for those cases, the time-headway distribution is determined by the flow regardless to the density. The qualitative comparison of the results with traffic data demonstrates that the genTASEP with backward order and attractive interaction evinces similar properties of time-headway distribution as the real traffic sample.

  15. The Braess Paradox in a network of totally asymmetric exclusion processes

    CERN Document Server

    Bittihn, Stefan

    2016-01-01

    We study the Braess paradox in the transport network as originally proposed by Braess with totally asymmetric exclusion processes (TASEPs) on the edges. The Braess paradox describes the counterintuitive situation where adding an additional edge to a road network leads to a user optimum with higher traveltimes for all network users. Traveltimes on the TASEPs are nonlinear in the density and jammed states can occur due to the microscopic exclusion principle. Furthermore the individual edges influence each other. This leads to a much more realistic description of traffic-like transport on the network than in previously studied linear macroscopic mathematical models. Furthermore the stochastic dynamics allows to explore the effects of fluctuations on the network performance. We observe that for low densities the added edge leads to lower traveltimes. For slightly higher densities the Braess paradox in its classical sense occurs in a small density regime. In a large regime of intermediate densities strong fluctuat...

  16. Total dynamic response of a PSS vehicle negotiating asymmetric road excitations

    Science.gov (United States)

    Zhu, Jian Jun; Khajepour, Amir; Esmailzadeh, Ebrahim

    2012-12-01

    A planar suspension system (PSS) is a novel automobile suspension system in which an individual spring-damper strut is implemented in both the vertical and longitudinal directions, respectively. The wheels in a vehicle with such a suspension system can move back and forth relative to the chassis. When a PSS vehicle experiences asymmetric road excitations, the relative longitudinal motion of wheels with respect to the chassis in two sides of the same axle are not identical, and thus the two wheels at one axle will not be aligned in the same axis. The total dynamic responses, including those of the bounce, pitch and the roll of the PSS vehicle, to the asymmetric road excitation may exhibit different characteristics from those of a conventional vehicle. This paper presents an investigation into the comprehensive dynamic behaviour of a vehicle with the PSS, in such a road condition, on both the straight and curved roads. The study was carried out using an 18 DOF full-car model incorporating a radial-spring tyre-ground contact model and a 2D tyre-ground dynamic friction model. Results demonstrate that the total dynamic behaviour of a PSS vehicle is generally comparable with that of the conventional vehicle, while PSS exhibits significant improvement in absorbing the impact forces along the longitudinal direction when compared to the conventional suspension system. The PSS vehicle is found to be more stable than the conventional vehicle in terms of the directional performance against the disturbance of the road potholes on a straight line manoeuvre, while exhibiting a very similar handling performance on a curved line.

  17. PEMODELAN TOTALLY ASYMMETRIC EXCLUSION PROCESS DUA DIMENSI UNTUK LALU LINTAS KENDARAAN PADA PERTIGAAN JALAN YANG SEARAH

    Directory of Open Access Journals (Sweden)

    R Septiana

    2014-06-01

    Full Text Available Abstrak __________________________________________________________________________________________ Penelitian ini mengkaji model dinamik yaitu Totally Asymmetric Exclusion Process (TASEP khususnya dalam dua dimensi (2D. Selain itu akan dibahas pula mengenai syarat batas dan aturan dinamika yang digunakan dalam pemodelan ini. TASEP telah diaplikasikan dalam berbagai bidang, salah satunya ialah pemodelan lalu lintas kendaraan (traffic flow. Sistem dua dimensi yang akan dikaji adalah sistem yang diskrit, yakni sistem ke kisi dua dimensi. Sistem ini dimodifikasi menjadi bentuk pertigaan (junction yang searah. Lebih jauh lagi, kendaraan yang melalui pertigaan dimodelkan sebagai partikel yang melompat dari satu kisi ke ke kisi yang lain. Nilai kepadatan dan rapat arus partikel dalam sistem tersebut ditentukan secara numerik. Persamaan kontinuitas untuk menggambarkan dinamika partikel dalam TASEP diselesaikan menggunakan metode Euler. Profil kepadatan dan rapat arus partikel dipengaruhi oleh laju masukan (input rate dan laju keluaran (output rate lompatan partikel.   Abstract __________________________________________________________________________________________ The research analyzed a dynamic model of Totally Asymmetric Exclusion Process (TASEP, especially in two dimensions (2D and  also the boundary and rules dynamic conditions  used in this modeling. TASEP has been applied in various fields, one of them is the modeling of vehicle traffic. Two-dimensional system that will be studied is the discrete system of two-dimensional lattice system. The system is modified into the form of unidirectional T-junction . Furthermore, the vehicles that pass the junction are modeled as particles that jump from one lattice to another lattice. The value of the density and current density of particles in the system is determined numerically. The continuity equation to describe the dynamics of particles in TASEP is solved by using Euler's method. The profiles of

  18. Synthesis and Catalytic Asymmetric Reaction of Chiral Pyridine Prolinol Derivatives

    Institute of Scientific and Technical Information of China (English)

    CHEN Xiao; ZHANG Yong-Xin; DU Da-Ming; HUA Wen-Ting

    2003-01-01

    @@ The enantioselective reduction of prochiral ketones with borane in the presence of a chiral ligand leading to enantiomerically pure secondary alcohols has received considerable attention in recent years. [1] Enantiomerically pure secondary alcohols are important intermediates for the synthesis of various other organic compounds such as halides, esters, ethers, ketones and amines. To the best of our knowledge, the use of pyridine prolinol derivatives in the reduction of ketones has not been reported so far. Thus, it should be of interest to investigate the catalytic a bility of such ligands. We have an ongoing project in the synthesis and application of chiral pyridine derivatives in chiral molecular recognition[2] and we want to evaluate the effect resulting from the introduction of a pyridinyl moiety onto the catalysts. We expect that the cooperation of pyridine unit and chiral prolinol unit in new ligands may result in unique properties for catalytic reaction.

  19. Stereoselective first total synthesis, confirmation of the absolute configuration and bioevaluation of botryolide-E.

    Science.gov (United States)

    Reddy, D Kumar; Shekhar, V; Prabhakar, P; Babu, D Chanti; Ramesh, D; Siddhardha, B; Murthy, U S N; Venkateswarlu, Y

    2011-02-01

    A simple, first stereoselective total synthesis of botryolide-E has been described. The synthesis started from propylene oxide employing Jacobsen's hydrolytic kinetic resolution (HKR), selective epoxide opening, sharpless asymmetric dihydroxylation, one pot acetonide deprotection and lactonization as key steps. Further, the synthesis confirms the absolute configuration of the natural product botryolide-E and we evaluated the biological behavior of natural product botryolide-E against a panel of bacteria and fungi. Botryolide-E exhibits significant potent activity against Staphylococcus aureus (MTCC 96) (6.25 μg/ml), good against Escherichia coli (MTCC 443) (12.5 μg/ml), Bacillus subtilis (MTCC 441) (25 μg/ml) and compound 1 exhibited good to moderate antifungal activity. PMID:21211971

  20. Total synthesis of (±)-divanillyltetrahydrofuran ferulate

    Indian Academy of Sciences (India)

    Ya-Mu Xia; Jia You; Qi Wang

    2010-05-01

    A convenient method for the synthesis of sesquilignan threo- and erythro-(±)-divanillyltetrahydrofuran ferulate is described. The synthesis was based on a unified synthetic strategy involving two Stobbe condensations to give the skeleton of lignan, and then reduction reaction to form meso- and threo-(±)-secoisolanciresinol. meso- and threo-(±)-secoisolanciresinol were separated by flash column chromatography, followed by intramolecular reaction with TsCl to afford the key intermediate meso- or threo-(±)-shonanin, then condensation with ferulaic acid to obtain sesquilignan threo- or its analogue erythro-(±)-divanillyltetrahydrofuran ferulate.

  1. IMMOBILIZATION OF Saccharomyces Cerevisiae USING POLY(ACRYLAMIDE) GEL FOR ASYMMETRIC SYNTHESIS OF R(-)-MANDELIC ACID

    Institute of Scientific and Technical Information of China (English)

    LI Zhongqin; GUO Daiping; HUANG Xinghua; YANG Kai; XU Xiaoping

    2006-01-01

    In this paper, the poly(acrylamide) hydrogel used to immobilize saccharomyces cerevisiae for asymmetric synthesis of R(-)-mandelic acid was prepared with free radical ploymerization in deionized water at room temperature under nitrogen atmosphere. The influence of the composition of hydrogel, loading amount of cells and culture conditions on the asymmetric synthesis was investigated. Results show that PAAm hydrogel is a feasible carrier for immobilization of cells which is a potential alternative method to prepare enantiomerically pure R(-)-mandelic acid.

  2. Synthesis of New Bifunctional Bis(oxazolines) and Their Application in the Asymmetric Cyanosilylation of Aromatic Ketones

    Institute of Scientific and Technical Information of China (English)

    LUO,Mei; DU,Da-Ming

    2004-01-01

    @@ Catalytic asymmetric synthesis of tertiary cyanohydrins by the addition of cyanide to a wide range of ketones has important synthetic utility, since the resulting optically active cyanohydrins are important intermediates for the synthesis of a variety of valuable classes of chiral compounds. The application of oxazoline in asymmetric cyanosilylation has seldom reported in comparation with other reactions.[1] Recently, polymer-supported pyridine-bis(oxazoline) ytterbium complex was reported to catalyze cyanosilylation of benzaldehyde.

  3. Collagen synthesis, nitric oxide and asymmetric dimethylarginine in diabetic subjects undergoing hyperbaric oxygen therapy

    OpenAIRE

    Gürdöl, Figen; Cimsit, M; Öner-Iyidoğan, Yıldız; Koçak, Hikmet; Sengun, S; Yalçınkaya-Demirsöz, S

    2010-01-01

    The main pathological condition in patients with impaired wound healing is diabetes mellitus. These patients have significantly low circulating nitric oxide (NO) levels because the stimulatory action of insulin on NO synthesis is absent. Additionally, asymmetric dimethylarginine (ADMA), an inhibitor of NO synthase, is increased owing to the generation of oxidative stress. NO was thought to contribute to wound healing. Hyperbaric oxygen (HBO) treatment is generally used in order to accelerate ...

  4. A Facile Method for Asymmetric Synthesis of β-Hydroxy-α-amino Acids

    Institute of Scientific and Technical Information of China (English)

    LI,Shuo; LI,Lei; ZHANG,Zhi-Hui; XU,Peng-Fei

    2004-01-01

    @@ β-Hydroxy-a-amino acids are an important class of amino acids due to their inherent biological investigations[1] and as structural components of more complex biomolecules.[2] β-Hydroxy-a-amino acids have been used as intermediates in the asymmetric synthesis of other compounds.[3] An efficient and convenient concise method for the preparation of optically pure enantiomers of β-hydroxy-α-amino acids would be of general interest.

  5. Asymmetric aerobic oxidative NHC-catalysed synthesis of dihydropyranones utilising a system of electron transfer mediators.

    Science.gov (United States)

    Axelsson, A; Hammarvid, E; Ta, L; Sundén, H

    2016-10-01

    In the context of green chemistry, the replacement of high molecular weight stoichiometric oxidants with O2 is most desirable but difficult. Here, we report the asymmetric aerobic oxidative synthesis of dihydropyranones. The oxidation is aided by a system of electron transfer mediators and is selective toward the homoenolate. The dihydropyranones can be isolated in high to excellent yields, with high ee (up to 95%). PMID:27604573

  6. Electroenzymatic strategies for deracemization, stereoinversion and asymmetric synthesis of amino acids

    Energy Technology Data Exchange (ETDEWEB)

    Maerkle, Wolfgang [Institut fuer Biotechnologie 2, Forschungszentrum Juelich GmbH, D-52425 Juelich (Germany); Luetz, Stephan [Institut fuer Biotechnologie 2, Forschungszentrum Juelich GmbH, D-52425 Juelich (Germany)], E-mail: s.luetz@fz-juelich.de

    2008-02-25

    A combination of a selective enzymatic oxidation with an unselective electrochemical reduction step was applied for deracemization, stereoinversion and asymmetric synthesis of L-leucine (starting from racemic leucine, D-leucine or 4-methyl-2-oxovaleric acid) in a batch reactor. D-Amino acid oxidase (D-AAO) from Trigonopsis variabilis was used as enzyme. Reaction conditions for the electrochemical and enzymatic reactions were investigated separately and finally combined to an electroenzymatic synthesis, yielding 3.5 mmol L{sup -1} d{sup -1} of L-leucine (ee 91%)

  7. Rational design and asymmetric synthesis of potent and neurotrophic ligands for FK506-binding proteins (FKBPs).

    Science.gov (United States)

    Pomplun, Sebastian; Wang, Yansong; Kirschner, Alexander; Kozany, Christian; Bracher, Andreas; Hausch, Felix

    2015-01-01

    To create highly efficient inhibitors for FK506-binding proteins, a new asymmetric synthesis for pro-(S)-C(5) -branched [4.3.1] aza-amide bicycles was developed. The key step of the synthesis is an HF-driven N-acyliminium cyclization. Functionalization of the C(5)  moiety resulted in novel protein contacts with the psychiatric risk factor FKBP51, which led to a more than 280-fold enhancement in affinity. The most potent ligands facilitated the differentiation of N2a neuroblastoma cells with low nanomolar potency.

  8. Concise Total Synthesis of Enigmazole A.

    Science.gov (United States)

    Ahlers, Andreas; de Haro, Teresa; Gabor, Barbara; Fürstner, Alois

    2016-01-22

    An efficient entry into the phosphorylated marine macrolide enigmazole A is described. Enigmazole A interferes with c-Kit signaling by an as yet unknown mode of action and is therefore a potential lead in the quest for novel anticancer agents. Key to success is a gold-catalyzed cascade comprising a [3,3]-sigmatropic rearrangement of a propargyl acetate along the periphery of a macrocyclic scaffold, followed by a transannular hydroalkoxylation of the resulting transient allenyl acetate. This transformation mandated the use of a chiral gold catalyst to ensure a matching double-asymmetric setting. Other noteworthy steps are the preparation of the oxazole building block by a palladium-catalyzed C-H activation, as well as the smooth ring-closing alkyne metathesis of a diyne substrate bearing a propargylic leaving group, which has only little precedent. PMID:26663132

  9. Total Synthesis of the Antitumor Antibiotic Basidalin.

    Science.gov (United States)

    Acosta, Jaime A M; Muddala, Ramesh; Barbosa, Luiz C A; Boukouvalas, John

    2016-08-01

    The first synthesis of the tetronamide antibiotic basidalin was accomplished in five steps and 39% overall yield from readily available 4-bromo-2-triisopropylsilyloxyfuran and 2-formyl-1,3-dithiane. Highlights include: (i) regio- and stereocontrolled assemblage of a pivotal (Z)-γ-ylidene-β-bromobutenolide intermediate by stereodirected vinylogous aldol condensation (SVAC), (ii) installation of the amino group via aza-Michael addition/elimination, and crucially (iii) facile access to basidalin by late-stage dithiane removal. PMID:27347696

  10. Total synthesis of (+)-gelsemine via an organocatalytic Diels-Alder approach.

    Science.gov (United States)

    Chen, Xiaoming; Duan, Shengguo; Tao, Cheng; Zhai, Hongbin; Qiu, Fayang G

    2015-01-01

    The structurally complex alkaloid gelsemine was previously thought to have no significant biological activities, but a recent study has shown that it has potent and specific antinociception in chronic pain. While this molecule has attracted significant interests from the synthetic community, an efficient synthetic strategy is still the goal of many synthetic chemists. Here we report the asymmetric total synthesis of (+)-gelsemine, including a highly diastereoselective and enantioselective organocatalytic Diels-Alder reaction, an efficient intramolecular trans-annular aldol condensation furnishing the prolidine ring and establishing the configuration of the C20 quaternary carbon stereochemical centre. The entire gelsemine skeleton was constructed through a late-stage intramolecular SN2 substitution. The enantiomeric excess of this total synthesis is over 99%, and the overall yield is around 5%. PMID:25995149

  11. Asymmetric synthesis of tetrahydroisoquinolines by enzymatic Pictet-Spengler reaction.

    Science.gov (United States)

    Nishihachijo, Masakatsu; Hirai, Yoshinori; Kawano, Shigeru; Nishiyama, Akira; Minami, Hiromichi; Katayama, Takane; Yasohara, Yoshihiko; Sato, Fumihiko; Kumagai, Hidehiko

    2014-01-01

    Norcoclaurine synthase (NCS) catalyzes the stereoselective Pictet-Spengler reaction between dopamine and 4-hydroxyphenylacetaldehyde as the first step of benzylisoquinoline alkaloid synthesis in plants. Recent studies suggested that NCS shows relatively relaxed substrate specificity toward aldehydes, and thus, the enzyme can serve as a tool to synthesize unnatural, optically active tetrahydroisoquinolines. In this study, using an N-terminally truncated NCS from Coptis japonica expressed in Escherichia coli, we examined the aldehyde substrate specificity of the enzyme. Herein, we demonstrate the versatility of the enzyme by synthesizing 6,7-dihydroxy-1-phenethyl-1,2,3,4-tetrahydroisoquinoline and 6,7-dihydroxy-1-propyl-1,2,3,4-tetrahydroisoquinoline in molar yields of 86.0 and 99.6% and in enantiomer excess of 95.3 and 98.0%, respectively. The results revealed the enzyme is a promising catalyst that functions to stereoselectively produce various 1-substituted-1,2,3,4-tetrahydroisoquinolines. PMID:25036970

  12. The Total Synthesis of 14-Deoxycrassin and Pseudoplexaurol: A Convergent Synthesis of Cyclization Precursor

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The synthesis of epoxy aldehyde 4, a cyclization precursor for the total synthesis of 14-deoxycrassin and pseudoplexaurol, starting from geraniol in a convergent and stereoselective manner, is described.

  13. First total synthesis of (+/-)-3-hydroxy-11-norcytisine

    DEFF Research Database (Denmark)

    Yohannes, Daniel; Hansen, Camilla Petrycer; Akireddy, Srinivasa Rao;

    2008-01-01

    The first total synthesis of the natural product 3-hydroxy-11-norcytisine ( 1), structurally related to cytisine ( 2), a benchmark ligand at neuronal nicotinic acetylcholine receptors (NNRs), has been achieved. The synthesis permits the unambiguous confirmation of the structure originally proposed...

  14. Total synthesis of the potent microtubule-stabilizing agent (+)-discodermolide.

    Science.gov (United States)

    Harried, Scott S; Lee, Christopher P; Yang, Ge; Lee, Tony I H; Myles, David C

    2003-08-22

    The total synthesis of the potent microtubule-stabilizing, antimitotic agent (+)-discodermolide is described. The convergent synthetic strategy takes advantage of the diastereoselective alkylation of a ketone enolate to establish the key C15-C16 bond. The synthesis is amenable to preparation of gram-scale quantities of (+)-discodermolide and analogues.

  15. Emergence of jams in the generalized totally asymmetric simple exclusion process.

    Science.gov (United States)

    Derbyshev, A E; Povolotsky, A M; Priezzhev, V B

    2015-02-01

    The generalized totally asymmetric exclusion process (TASEP) [J. Stat. Mech. (2012) P05014] is an integrable generalization of the TASEP equipped with an interaction, which enhances the clustering of particles. The process interpolates between two extremal cases: the TASEP with parallel update and the process with all particles irreversibly merging into a single cluster moving as an isolated particle. We are interested in the large time behavior of this process on a ring in the whole range of the parameter λ controlling the interaction. We study the stationary state correlations, the cluster size distribution, and the large-time fluctuations of integrated particle current. When λ is finite, we find the usual TASEP-like behavior: The correlation length is finite; there are only clusters of finite size in the stationary state and current fluctuations belong to the Kardar-Parisi-Zhang universality class. When λ grows with the system size, so does the correlation length. We find a nontrivial transition regime with clusters of all sizes on the lattice. We identify a crossover parameter and derive the large deviation function for particle current, which interpolates between the case considered by Derrida-Lebowitz and a single-particle diffusion. PMID:25768476

  16. One-Pot Catalysis Using a Chiral Iridium Complex/Brønsted Base: Catalytic Asymmetric Synthesis of Catalponol.

    Science.gov (United States)

    Suzuki, Takeyuki; Ismiyarto; Ishizaka, Yuka; Zhou, Da-Yang; Asano, Kaori; Sasai, Hiroaki

    2015-11-01

    Tandem asymmetric hydrogen transfer oxidation/aldol condensation under relay catalysis of a chiral iridium complex/achiral Brønsted base binary system is described for the synthesis of α-benzylidene-γ-hydroxytetralones with high ee's. A two-step synthesis of catalponol was achieved using this sequential methodology together with regio- and stereoselective hydroboration. PMID:26496409

  17. Total synthesis: Towards artificial terpene cyclases

    Science.gov (United States)

    Willot, Matthieu; Christmann, Mathias

    2010-07-01

    The plant-derived sesquiterpene englerin A is a potent inhibitor of several renal cancer cell lines. Two recent total syntheses have utilized cationic gold(I)-complexes to coax readily available open-chain precursors into englerin's challenging oxotricyclic core with enzyme-like precision.

  18. Palladium-catalyzed asymmetric alkylation in the synthesis of cyclopentanoid and cycloheptanoid core structures bearing all-carbon quaternary stereocenters

    KAUST Repository

    Hong, Allen Y.

    2011-12-01

    General catalytic asymmetric routes toward cyclopentanoid and cycloheptanoid core structures embedded in numerous natural products have been developed. The central stereoselective transformation in our divergent strategies is the enantioselective decarboxylative alkylation of seven-membered β-ketoesters to form α-quaternary vinylogous esters. Recognition of the unusual reactivity of β-hydroxyketones resulting from the addition of hydride or organometallic reagents enabled divergent access to γ-quaternary acylcyclopentenes through a ring contraction pathway or γ-quaternary cycloheptenones through a carbonyl transposition pathway. Synthetic applications of these compounds were explored through the preparation of mono-, bi-, and tricyclic derivatives that can serve as valuable intermediates for the total synthesis of complex natural products. This work complements our previous work with cyclohexanoid systems.

  19. First total synthesis of (±)-abyssinoflavanone V

    Institute of Scientific and Technical Information of China (English)

    Jin Hui Yang; Yan Min Zhao; Cong Bin Ji

    2008-01-01

    The total synthesis of (±)-abyssinoflavanone V was first achieved through C-prenylation, selective protection of phenolic hydroxyl group, aldol condensation, cyclization and deprotection starting from cheap 4-hydroxybenzaldehyde and 2,4,6-trihydroxyacetophenone, with total yield 24%. All structures of new compounds were confirmed by IR, 1H NMR and MS.

  20. First total synthesis of (±)-sepicanin A

    Institute of Scientific and Technical Information of China (English)

    Jin Hui Yang; Wen Qian Huang; Jun Shan Luo; Dong Dong Guo; Yu Heng Zhang; Hong Jun Li

    2012-01-01

    A facile approach for the first total synthesis of naturally occurring geranylated flavanoids sepicanin A has been obtained with total yield 16% starting from 2,4,6-trihydroxyacetophenone after four steps.The key step was the protic acids (HCl or p-TsOH)-catalyzed benzopyrone formation in a protic polar solvent by deprotection and cyclization of chalcone in one step.

  1. A New Complex with Good Catalytic Properties in Asymmetric Synthesis of Cyclopropanecarboxylic Acids

    Institute of Scientific and Technical Information of China (English)

    CAI Ya; ZHENG He-Gen; XIN Xin-Quan

    2003-01-01

    @@ The chemistry of transition metal-sulfur clusters has attracted much attention recently owing to their relevance to certain biological and industrial catalyses, rich structural chemistry, and special reactive properties as well as potential application in nonlinear optical materials. [1~ 3] In this article, a new complex, WCu2S4 (dppf)2 [ dppf = 1, 1′bis(diphenylphosphino)ferrocene] was synthesized through solid state reaction, and it was found that this complex had good catalytic properties in asymmetric synthesis of cyclopropanecarboxylic acids.

  2. Synthesis of Novel Chiral Dibenzo [ a, c ] cycloheptadiene Bis(oxazoline) and Catalytic Asymmetric Reactions

    Institute of Scientific and Technical Information of China (English)

    FU Bin; DU Da-Ming; WANG Jian-Bo

    2003-01-01

    @@ Over the last decade, C2-symmetric chiral oxazoline metal complexes have been recognized as an effective classof chiral catalyst in a variety of transition metal catalyzed asymmetric reactions. [1] High catalytic activities and enantiomeric excesses have been obtained using C2-symmetric chiral ligands in conjunction with suitable transition metal ion, for example, the hydrosilylation of ketone, allylic alkylation, Michael addition, Diels-Alder cycloaddition, and cyclopropanation. Thus, the design and synthesis of new chiral oxazoline ligands have inspired many scientists to work with great efforts.

  3. One-Pot, Four-Step Organocatalytic Asymmetric Synthesis of Functionalized Nitrocyclopropanes.

    Science.gov (United States)

    Zaghi, Anna; Bernardi, Tatiana; Bertolasi, Valerio; Bortolini, Olga; Massi, Alessandro; De Risi, Carmela

    2015-09-18

    The asymmetric synthesis of functionalized nitrocyclopropanes has been achieved by a one-pot, four-step method catalyzed by (S)-diphenylprolinol TMS ether, which joins two sequential domino reactions, namely a domino sulfa-Michael/aldol condensation of α,β-unsaturated aldehydes with 1,4-dithiane-2,5-diol, and a domino Michael/α-alkylation reaction of the derived chiral dihydrothiophenes with bromonitromethane. The title compounds were obtained in 27-45% yields, with high levels of diastereoselectivity (93:7 to 100:0 dr) and generally good enantioselectivities (up to 95:5 er). PMID:26317611

  4. THE ASYMMETRIC SYNTHESIS OF AMINO ACIDS UNDER POLYMER-SUPPORTED PHASE TRANSFER CATALYTIC CONDITION

    Institute of Scientific and Technical Information of China (English)

    1998-01-01

    The optical α-amino acids were synthesized under room temperature by alkylation of N-(diphenyl methylene) glycine t-butyl ester under polymer-supported phase transfer conditions using polymer-supported cinchonine (or quinine) alkaloids as chiral phase transfer catalysts and dichloromethane as solvent, followed by hydrolysis of the above intermediates introduced to the final products-optical α-amino acids. This is a new method for the asymmetric synthesis of α-amino acids. The influences of catalyst,temperature, substrates, and organic solvents on the chemical yield and optical purities of products were studied.

  5. Asymmetric synthesis of -aminophosphonates: The bio-isosteric analogs of -aminobutyric acid

    Indian Academy of Sciences (India)

    Kalisankar Bera; Dwayaja Nadkarni; Iirishi N N Namboothiri

    2013-05-01

    The properties of aminophosphonates as transition state analogs of amino acids, and as antibacterial, antifungal and antiHIV agents attracted considerable attention in recent years. Although many reviews appeared in the literature covering - and -aminophosphonates, -aminophosphonates did not receive sufficient attention despite the fact that parent -aminophosphonic acid and its derivatives are bio-isosteric analogs of GABA (-amino butyric acid). This review provides a critical summary of the significance of -aminophosphonates and various approaches to their synthesis, with particular emphasis to asymmetric versions.

  6. Total synthesis and stereochemical revision of (+)-aeruginosin 298-A.

    Science.gov (United States)

    Wipf, P; Methot, J L

    2000-12-28

    [structure:see text] Novel routes toward both enantiomers of the bicyclic proline surrogate 2-carboxy-6-hydroxyoctahydroindole, i.e., Choi, were developed on the basis of the oxidative cyclization of L-tyrosine. Synthesis of the proposed sequence of (+)-aeruginosin 298-A did not provide the natural product. Incorporation of a D-leucine residue, in contrast, led to the total synthesis of this thrombin inhibitor. PMID:11150202

  7. Total Synthesis and Absolute Configuration of the Marine Norditerpenoid Xestenone

    Directory of Open Access Journals (Sweden)

    Hiroaki Miyaoka

    2009-11-01

    Full Text Available Xestenone is a marine norditerpenoid found in the northeastern Pacific sponge Xestospongia vanilla. The relative configuration of C-3 and C-7 in xestenone was determined by NOESY spectral analysis. However the relative configuration of C-12 and the absolute configuration of this compound were not determined. The authors have now achieved the total synthesis of xestenone using their developed one-pot synthesis of cyclopentane derivatives employing allyl phenyl sulfone and an epoxy iodide as a key step. The relative and absolute configurations of xestenone were thus successfully determined by this synthesis.

  8. Effect of plate asymmetric rolling parameters on the change of the total unit pressure of roll

    Directory of Open Access Journals (Sweden)

    A. Kawalek

    2011-07-01

    Full Text Available This work shows the results of theoretical analysis of asymmetric rolling process of plates in the finishing mill of plate rolling. Its aim was to determine the influence of asymmetry velocity of working rolls on decrease of unit pressure of metal on the rolls. The lower value of the unit pressure will reduce the elastic deflection of the finishing stand and improve the cross-section shape of plate. Three-dimensional simulation of asymmetric hot rolling of S355J2G3 steel plates was done with the aid of FORGE 2008® software. The tensor polynomial interpolation was used for comparing the values of the unit pressure obtaining from symmetric and asymmetric rolling.

  9. Asymmetric synthesis of telcagepant, a CGRP receptor antagonist for the treatment of migraine.

    Science.gov (United States)

    Xu, Feng; Zacuto, Michael; Yoshikawa, Naoki; Desmond, Richard; Hoerrner, Scott; Itoh, Tetsuji; Journet, Michel; Humphrey, Guy R; Cowden, Cameron; Strotman, Neil; Devine, Paul

    2010-11-19

    A highly efficient, asymmetric synthesis of telcagepant (1), a CGRP receptor antagonist for the treatment of migraine, is described. This synthesis features the first application of iminium organocatalysis on an industrial scale. The key to the success of this organocatalytic transformation was the identification of a dual acid cocatalyst system, which allowed striking a balance of the reaction efficiency and product stability effectively. As such, via an iminium species, the necessnary C-6 stereogenicity was practically established in one operation in >95% ee. Furthermore, we enlisted an unprecedented Doebner-Knoevenagel coupling, which was also via an iminium species, to efficiently construct the C3-C4 bond with desired functionality. In order to prepare telcagepant (1) in high quality, a practical new protocol was discovered to suppress the formation of desfluoro impurities formed under hydrogenation conditions to manufacturing process and prepares telcagepant (1) with the high quality required for pharmaceutical use.

  10. Synthesis and photophysicochemical studies of poly(ethylene glycol) conjugated symmetrical and asymmetrical zinc phthalocyanines

    Science.gov (United States)

    Dinçer, Hatice; Mert, Humeyra; Çalışkan, Emel; Atmaca, Göknur Yaşa; Erdoğmuş, Ali

    2015-12-01

    Synthesis and characterization of poly(ethylene glycol) conjugated symmetrical and asymmetrical zinc phthalocyanines (ZnPcs) is described. Copper (I) catalyzed azide-alkyne cycloaddition (CuAAC) click reaction between azide functional methoxypoly(ethylene glycol) (mPEG-N3) and tetra terminal alkynyl substituted ZnPc yields star polymer with ZnPc core. Furthermore, CuAAC click reaction between asymmetrically terminal alkynyl substituted zinc phthalocyanine (aZnPc) and mPEG-N3 yields aZnPc end functionalized PEG. Spectral, photophysical (fluorescence quantum yield), photochemical (singlet oxygen (ΦΔ), and photodegradation quantum yield (Φd) properties of the symmetrically, and asymmetrically PEGylated ZnPcs are investigated to be used as sensitizers in photodynamic therapy (PDT). The quantum yield values of fluorescence (ΦF) and singlet oxygen generation (ΦΔ) for water soluble symmetrically PEGylated ZnPc in aqueous solution are calculated as 0.01 and 0.14 respectively, suggesting its potential as photosensitizer in PDT treatment.

  11. [Asymmetric synthesis of aromatic L-amino acids catalyzed by transaminase].

    Science.gov (United States)

    Xia, Wenna; Sun, Yu; Min, Cong; Han, Wei; Wu, Sheng

    2012-11-01

    Aromatic L-Amino acids are important chiral building blocks for the synthesis of many drugs, pesticides, fine chemicals and food additives. Due to the high activity and steroselectivity, enzymatic synthesis of chiral building blocks has become the main research direction in asymmetric synthesis field. Guided by the phylogenetic analysis of transaminases from different sources, two representative aromatic transaminases TyrB and Aro8 in type I subfamily, from the prokaryote Escherichia coli and eukaryote Saccharomyces cerevisia, respectively, were applied for the comparative study of asymmetric transamination reaction process and catalytic efficiency of reversely converting keto acids to the corresponding aromatic L-amino acid. Both TyrB and Aro8 could efficiently synthesize the natural aromatic amino acids phenylalanine and tyrosine as well as non-natural amino acid phenylglycine. The chiral HPLC analysis showed the produced amino acids were L-configuration and the e.e value was 100%. L-alanine was the optimal amino donor, and the transaminase TyrB and Aro8 could not use D-amino acids as amino donor. The optimal molar ratio of amino donor (L-alanine) and amino acceptor (aromatic alpha-keto acids) was 4:1. Both of the substituted group on the aromatic ring and the length of fatty acid carbon chain part in the molecular structure of aromatic substrate alpha-keto acid have the significant impact on the enzyme-catalyzed transamination efficiency. In the experiments of preparative-scale transamination synthesis of L-phenylglycine, L-phenylalanine and L-tyrosine, the specific production rate catalyzed by TryB were 0.28 g/(g x h), 0.31 g/(g x h) and 0.60 g/(g x h) and the specific production rate catalyzed by Aro8 were 0.61 g/(g x h), 0.48 g/(g x h) and 0.59 g/(g x h). The results obtained here were useful for applying the transaminases to asymmetric synthesis of L-amino acids by reversing the reaction balance in industry.

  12. Competitive exclusion principle in ecology and absolute asymmetric synthesis in chemistry.

    Science.gov (United States)

    Ribó, Josep M; Hochberg, David

    2015-10-01

    The key concepts underlying the Frank model (1953) for spontaneous asymmetric synthesis in chemistry are traced back to the pioneering works of Volterra (1926) and Lotka (1932) on biological species competition. The Lotka-Volterra (L-V) two-species exclusive competition model reduces to the Frank model for the special case of distinguishable but degenerate species (i.e., the enantiomers). The important ecological principle of competitive exclusion, originally derived from the L-V two-competitors model, is a consequence of sufficiently antagonistic interactions between the species competing for limited common resources, or mutual inhibition, as the term is known in the chemical literature on absolute asymmetric synthesis. The L-V and Frank models are described by the same general differential equations, nevertheless a crucial thermodynamic distinction between these models is necessary to correlate ecological selection and chemical selectivity arising from 1) the absence of reversibility in biological transformations, in marked contrast to chemical reactions, and 2) the constraints in chemical scenarios on the reaction rate constants required to fulfill the principle of micro-reversibility. PMID:26301597

  13. Total Synthesis of Three New Dihydrostilbenes from Bulbophllum odoratissimum

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    A total synthesis of three new dihydrostilbenes, 1, 2 and 3, which were isolated from Bulbophyllum odoratissimum Lindl. with significant cytotoxicity toward human cancer cell lines,was developed via Horner reaction etc. The natural products 1, 2 and 3 were obtained in 5.8%,6.6% and 5.9%, respectively.

  14. The First Total Synthesis of Triprenylquinone and Hydroquinones

    Institute of Scientific and Technical Information of China (English)

    Chun Hong LI; Xue Song CHEN; Guang Lian ZHOU; Zhi Xiang XIE; Ying LI

    2005-01-01

    First total synthesis of triprenylquinone and hydroquinones, three naturally occurring compound 1, 2 and (±) 3, have been achieved from readily available 2-bromo-5-methyl-1,4-dimethoxybenzene 4 and geranyl bromide. The triprenylquinone and hydroquinones precursor were readily prepared with use of a Julia reaction.

  15. Expedient total synthesis of pyrrothine natural products and analogs

    DEFF Research Database (Denmark)

    Hjelmgaard, Thomas; Givskov, Michael Christian; Nielsen, John

    2007-01-01

    This paper describes an expedient and straightforward total synthesis of the two pyrrothine natural products holomycin (7 steps, 11% overall) and xenorhabdin I (7 steps, 11% overall) and analogs thereof via a common late-stage intermediate. The pathway proceeds via the pyrrothine hydrochloride...

  16. Enantioselective Total Synthesis of the (+) Antipode of Zeylenone

    Institute of Scientific and Technical Information of China (English)

    An LIU; Zhan Zhu LIU; Zhong Mei ZOU; Shi Zhi CHEN; Li Zhen XU; Shi Lin YANG

    2004-01-01

    Starting from shikimic acid, the total synthesis of zeylenone was studied. The product was proved to be the (+)antipode of zeylenone through analysis and comparison of their respective spectra (including NMR, MS, IR and CD) and optical data. The absolute configuration of the natural product was thus determined to be (1 S,2S,3R).

  17. The total synthesis of 3b-hydroxynagilactone F

    NARCIS (Netherlands)

    Reuvers, J.T.A.

    1985-01-01

    The investigations described in this thesis deal with the total synthesis of physiologically active nor- and bisnorditerpenoid dilactones (fig.1).The goal was to design a synthetic route for this class of natural products and its derivatives. From a retrosynthe

  18. An asymmetric pericyclic cascade approach to oxindoles

    OpenAIRE

    Richmond, Edward

    2014-01-01

    The research in this thesis describes an asymmetric pericyclic cascade approach to the synthesis of a range of enantioenriched oxindoles using enantiopure oxazolidine derived nitrones and disubstituted ketenes. Chapter 1 aims to place this work in the context of the literature, describing other commonly employed or state-of-the-art asymmetric approaches to oxindoles and related compounds. Examples of where these approaches have been used successfully in the total synthesis of related indol...

  19. Asymmetric structure of germanene on an Al(111) surface studied by total-reflection high-energy positron diffraction

    Science.gov (United States)

    Fukaya, Yuki; Matsuda, Iwao; Feng, Baojie; Mochizuki, Izumi; Hyodo, Toshio; Shamoto, Shin-ichi

    2016-09-01

    The structure of germanene on an Al(111) surface has been experimentally investigated using the total-reflection high-energy positron diffraction (TRHEPD) method. The observed spot intensities are asymmetric, revealing no mirror symmetry in the atomic coordinates of germenene with respect to the direction. Quantitative TRHEPD rocking curve analysis, based on dynamical diffraction theory, has revealed that the germanene layer has a 3 × 3 structure with asymmetrical buckling due to the protrusion of one of the Ge atoms in the unit cell, which is unlike the structural model proposed in previous studies. The magnitude of the buckling was found to be 0.94 Å, and the spacing between the germanene and the Al(111) substrate to be 2.51 Å. The new structure proposed in the present investigations, though different from that reported in studies before, does not contradict the other characteristics which were found experimentally in the previous studies.

  20. Asymmetric Synthesis of (R)-Fluoxetine: A Practical Approach Using Recyclable and in-situ Generated Oxazaborolidine Catalyst

    Institute of Scientific and Technical Information of China (English)

    PADIYA Kamlesh; GAGARE Pravin; GAGARE Manjiri; LAL Bansi

    2009-01-01

    A practical route for the synthesis of (R)-fluoxetine·HCl (ee=96%) in 56% overall yield was described. The key intermediate (R)-3-chloro-1-phenyl--propanol was obtained by the asymmetric reduction of prochiral 3-chloropropiophenone using in-situ generated oxazaborolidine catalyst derived from (S)-α,α-diphenylprolinol. The chiral procatalyst (S)-α,α-diphenylprolinol was recovered quantitatively and recycled. An improved practical syn-thesis of (S)-α,α-diphenylprolinol was also discussed.

  1. Application of cyclic phosphonamide reagents in the total synthesis of natural products and biologically active molecules

    OpenAIRE

    Thilo Focken; Stephen Hanessian

    2014-01-01

    A review of the synthesis of natural products and bioactive compounds adopting phosphonamide anion technology is presented highlighting the utility of phosphonamide reagents in stereocontrolled bond-forming reactions. Methodologies utilizing phosphonamide anions in asymmetric alkylations, Michael additions, olefinations, and cyclopropanations will be summarized, as well as an overview of the synthesis of the employed phosphonamide reagents.

  2. Concise total synthesis and structural revision of (+)-pestalazine B.

    Science.gov (United States)

    Pérez-Balado, Carlos; de Lera, Angel R

    2010-11-21

    A convergent synthesis of the proposed structure of (+)-pestalazine B has been achieved in 4 steps using the N-alkylation of an unprotected tryptophan diketopiperazine with a 3a-bromopyrrolidinoindoline as the key step. Although its structure was confirmed by X-ray analysis, the spectroscopic data did not match those of the natural product. The versatility of the methodology allowed the preparation of several diastereomers, and the database generated led to the proposal of an isomeric structure for the natural alkaloid where the d-leucine and d-phenylalanine residues exchanged positions, which was corroborated by total synthesis. PMID:20848034

  3. Total Synthesis of Putative 11-epi-Lyngbouilloside Aglycon.

    Science.gov (United States)

    Kolleth, Amandine; Gebauer, Julian; ElMarrouni, Abdelatif; Lebeuf, Raphael; Prévost, Céline; Brohan, Eric; Arseniyadis, Stellios; Cossy, Janine

    2016-01-01

    We report here the total synthesis of 11-epi-lyngbouilloside aglycon. Our strategy features a Boeckman-type esterification followed by a RCM to form the 14-membered ring macrolactone and a late-stage side chain introduction via a Wittig olefination. Overall, the final product was obtained in 20 steps and 2% overall yield starting from commercially available 3-methyl-but-3-enol. Most importantly, the strategy employed is versatile enough to eventually allow us to complete the synthesis of the natural product and irrevocably confirm its structure. PMID:27556024

  4. Total Synthesis of Putative 11-epi-Lyngbouilloside Aglycon

    Science.gov (United States)

    Kolleth, Amandine; Gebauer, Julian; ElMarrouni, Abdelatif; Lebeuf, Raphael; Prévost, Céline; Brohan, Eric; Arseniyadis, Stellios; Cossy, Janine

    2016-01-01

    We report here the total synthesis of 11-epi-lyngbouilloside aglycon. Our strategy features a Boeckman-type esterification followed by a RCM to form the 14-membered ring macrolactone and a late-stage side chain introduction via a Wittig olefination. Overall, the final product was obtained in 20 steps and 2% overall yield starting from commercially available 3-methyl-but-3-enol. Most importantly, the strategy employed is versatile enough to eventually allow us to complete the synthesis of the natural product and irrevocably confirm its structure. PMID:27556024

  5. A Novel Asymmetric Synthesis of (-)-cis-1, 3-Dibenzylhexahydrofuro[3, 4-d]imidazole-2,4-dione

    Institute of Scientific and Technical Information of China (English)

    Wei Hua HAN; Hao Ran LI

    2005-01-01

    (-)-cis-1, 3-Dibenzyl-hexahydrofuro[3, 4-d]imidazole-2, 4-dione was prepared by a new synthesis method from meso dicarboxylic acid and dehydroabietylamine by asymmetric reduction in good yield with up to 91.6% e.e. value.

  6. Synthesis of boron/nitrogen substituted carbons for aqueous asymmetric capacitors

    Energy Technology Data Exchange (ETDEWEB)

    Tomko, Timothy [Energy and Mineral Engineering, Pennsylvania State University, University Park, PA 16802 (United States); Rajagopalan, Ramakrishnan, E-mail: rur12@psu.edu [Materials Research Institute, Pennsylvania State University, 270 MRL Bldg., University Park, PA 16802 (United States); Aksoy, Parvana [Energy Institute, Pennsylvania State University, University Park, PA 16802 (United States); Foley, Henry C. [Department of Chemical Engineering, The Pennsylvania State University, University Park, PA 16802 (United States)

    2011-06-01

    Highlights: > Synthesis of highly substituted boron and nitrogen containing carbons (BCN) for ultracapacitor applications. > Evidence for strong electroadsorption of protons on BCN. > Increased specific capacitance per unit area and improved cell voltage in aqueous asymmetric capacitors. - Abstract: Boron/nitrogen substituted carbons were synthesized by co-pyrolysis of polyborazylene/coal tar pitch blends to yield a carbon with a boron and nitrogen content of 14 at% and 10 at%, respectively. The presence of heteroatoms in these carbons shifted the hydrogen evolution overpotential to -1.4 V vs Ag/AgCl in aqueous electrolytes, providing a large electrochemical potential window ({approx}2.4 V) as well as a specific capacitance of 0.6 F/m{sup 2}. An asymmetric capacitor was fabricated using the as-prepared low surface area carbon as the negative electrode along with a redox active manganese dioxide as the positive electrode. The energy density of the capacitor exceeded 10 Wh/kg at a power density of 1 kW/kg and had a cycle life greater than 1000 cycles.

  7. Total Synthesis of Six 3,4-Unsubstituted Coumarins

    Directory of Open Access Journals (Sweden)

    Wenqing Gao

    2013-12-01

    Full Text Available In this article we describe a new methodology for the total synthesis of 3,4-unsubstituted coumarins from commercially available starting materials. Six examples were prepared, including five naturally occurring coumarins—7-hydroxy-6,8-dimethoxy-coumarin (isofraxidin, 7-hydroxy-6-methoxycoumarin (scopoletin, 6,7,8-trimethoxy-coumarin, 6,7-dimethoxycoumarin (scoparone, and 7,8-dihydroxycoumarin (daphnetin and one synthetic coumarin, 7-hydroxy-6-ethoxycoumarin. Moreover, five important o-hydroxybenzaldehyde intermediates were also obtained, namely 2,4-dihydroxy-3,5-dimethoxybenzaldehyde, 2,4-dihydroxy-5-methoxybenzaldehyde, 5-ethoxy-2,4-dihydroxy-benzaldehyde, 2-hydroxy-3,4,5-trimethoxybenzaldehyde, and 2-hydroxy-4,5-dimethoxy-benzaldehyde. The method developed herein involves just three or four steps and allows for the rapid synthesis of these important molecules in excellent yields. This is the first synthesis of 6,7,8-trimethoxycoumarin and 7-hydroxy-6-ethoxycoumarin.

  8. Short, Enantioselective Total Synthesis of Highly Oxidized Taxanes.

    Science.gov (United States)

    Yuan, Changxia; Jin, Yehua; Wilde, Nathan C; Baran, Phil S

    2016-07-11

    In the realm of natural product chemistry, few isolates have risen to the level of fame justifiably accorded to Taxol (1) and its chemical siblings. This report describes the most concise route to date for accessing the highly oxidized members of this family. As representative members of taxanes containing five oxygen atoms, decinnamoyltaxinine E (2) and taxabaccatin III (3), have succumbed to enantioselective total synthesis for the first time in only 18 steps from a simple olefin starting material. The strategy holistically mimics nature's approach (two-phase synthesis) and features a carefully choreographed sequence of stereoselective oxidations and a remarkable redox-isomerization to set the key trans-diol present in 2 and 3. This work lays the critical groundwork necessary to access even higher oxidized taxanes such as 1 in a more practical fashion, thus empowering a medicinal chemistry campaign that is not wedded to semi-synthesis. PMID:27240325

  9. Synthesis of asymmetric supramolecular compounds using a Ni(0) catalysed homo-coupling approach.

    Science.gov (United States)

    Cassidy, Lynda; Horn, Sabine; Cleary, Laura; Halpin, Yvonne; Browne, Wesley R; Vos, Johannes G

    2009-05-28

    The synthesis and characterisation of a series of dinuclear ruthenium and osmium polypyridyl metal complexes based on the bridging ligands [5-(5'-bipyridin-2',2''-yl)-3-(pyridin-2-yl)]-1,2,4-triazole (Hpytr-bipy), 2,2'-bis(pyridin-2''yl)-5,5'-bis(pyridin-3''-yl) (bipy-bipy) and 5,5'-bis(pyridin-2''-yl)-3,3'-bis(1,2,4-triazole) (Hpytr-Hpytr) are reported. The dinuclear complexes have been synthesised via a Ni(0) catalysed cross-coupling reaction from brominated precursors. With this approach a mixture of three products is obtained, which are separated by chromatographic methods. The compounds obtained are characterised by elemental analysis, (1)H NMR, absorption and emission spectroscopy. The synthetic approach developed offers a new route to asymmetric multinuclear supramolecular structures that is complimentary to the complexes as ligands/complexes as metal approaches. PMID:19440590

  10. Crotylsilane reagents in the synthesis of complex polyketide natural products: total synthesis of (+)-discodermolide.

    Science.gov (United States)

    Arefolov, Alexander; Panek, James S

    2005-04-20

    An efficient, highly convergent stereocontrolled synthesis of (+)-discodermolide has been achieved with 2.1% overall yield (27 steps longest linear sequence). The absolute stereochemistry of the C1-C6 (12), C7-C14 (13), and C15-C24 (11) subunits was introduced using asymmetric crotylation methodology. Key elements of the synthesis include the use of hydrozirconation-cross-coupling methodology for the construction of C13-C14 (Z)-olefin, acetate aldol reaction to construct the C6-C7 bond and install the C7 stereocenter with high levels of 1,5-anti stereoinduction, and the use of palladium-mediated sp(2)-sp(3) cross-coupling reaction to join the advanced fragments, which assembled the carbon framework of discodermolide.

  11. Catalytic asymmetric synthesis of butane diacetal-protected (4S,5S)-dihydroxycyclohexen-1-one and use in natural product synthesis.

    Science.gov (United States)

    Burns, David J; Hachisu, Shuji; O'Brien, Peter; Taylor, Richard J K

    2012-10-14

    Due to the lack of availability of unnatural (+)-quinic acid as a starting material, a 6-step synthesis of butane diacetal-protected (4S,5S)-dihydroxycyclohexen-1-one (formally derived from (+)-quinic acid) has been devised. The key catalytic asymmetric step involves a chiral Co-salen-catalysed epoxide ring-opening reaction. (4S,5S)-Dihydroxycyclohexen-1-one was utilised in the synthesis of two cyclohexenone natural products isolated from the mycelia of Lasiodiplodia theobromae. PMID:22930235

  12. Xenicane Natural Products: Biological Activity and Total Synthesis.

    Science.gov (United States)

    Betschart, Leo; Altmann, Karl-Heinz

    2015-01-01

    The xenicanes are a large class of mostly bicyclic marine diterpenoids featuring a cyclononane ring as a common structural denominator. After a brief introduction into the characteristic structural features of xenicanes and some biogenetic considerations, the major focus of this review will be on the various biological activities that have been reported for xenicanes and on efforts towards the total synthesis of these structures. Several xenicanes have been shown to be potent antiproliferative agents in vitro, but activities have also been reported in relation to inflammatory processes. However, so far, data on the possible in vivo activity of xenicanes are lacking. The major challenge in the total synthesis of xenicanes is the construction of the nine-membered ring. Different strategies have been pursued to establish this crucial substructure, including Grob fragmentation, ring-closing olefin metathesis, or Suzuki cross coupling as the enabling transformations. PMID:26429717

  13. Development of a Novel, Oxidatively Activated, Safety-Catch Linker for Solid-Phase Asymmetric Organic Synthesis (SPOS)

    Institute of Scientific and Technical Information of China (English)

    LIN,Jun; Hjalmar Skarphedinsson; Stepehen G.Davies

    2004-01-01

    @@ Solid-phase asymmetric organic synthesis has become a very important synthetic strategy within the organic chemistry community.[1] Critical to success in SPOS is a linking strategy which allows both the substrate to be loaded and the product released efficiently from the polymeric support. A safety catch linker[2] (SCL) is in principle a linking molecule orthogonal to the reaction conditions of the library synthesis, which can be easily activated by a simple chemical transformation to allow efficient cleavage of the products from the polymer under mild conditions. In order to introduce the SuperQuat chiral auxiliaries[3] for SOPS, we report herein design and synthesis of a novel safety catch linker for asymmetric conjugate addition reactions.

  14. Total synthesis of an oxepine natural product, (±)-janoxepin.

    Science.gov (United States)

    Doveston, Richard G; Steendam, René; Jones, Stuart; Taylor, Richard J K

    2012-02-17

    The total synthesis of (±)-janoxepin, a novel antiplasmodial d-leucine derived oxepine-pyrimidinone-ketopiperazine isolated from the fungus Aspergillus janus, is described. The cornerstones of the synthetic route are pyrimidinone preparation, ring-closing metathesis, aldol introduction of the enamide, and dihydro-oxepine elaboration. This synthetic route proved very efficient for the formation of a number of janoxepin analogues, including dihydro-janoxepin and tetrahydro-janoxepin. PMID:22288766

  15. Total synthesis and development of bioactive natural products

    OpenAIRE

    TATSUTA, Kuniaki

    2008-01-01

    The first total synthesis and development of a variety of bioactive natural products have been accomplished by using carbohydrates as a chiral source. In addition, practically useful intermediates have been created, analogs of natural products have been prepared, their structure-activity relationships studied, and the large-scale preparations of medicinally useful compounds established. The key target molecules have been the “Big Four” antibiotics (macrolides, aminoglycosides, β-lactams and t...

  16. First total synthesis of two nematicidal prenylated flavanones

    Institute of Scientific and Technical Information of China (English)

    Jin Hui Yang; Shi Zhi Jiang; Yan Min Zhao; Yun Feng Li; Cong Bin Ji; Wan Yi Liu

    2009-01-01

    The total synthesis of(±)-8-(3-methylbut-2-enyl)-2-phenyl-2,3-dihydrochromen-4-one and(±)-2-(4-hydroxyphenyl)-8-(3-methylbut-2-enyl)-2,3-dihydrochromen-4-one was first achieved through C-prenylation,protection of phenolic hydroxyl group,aldol condensation,cyclization and deprotection starting from cheap benzaldehyde,4-hydroxybenzaldehyde and 2-hydroxyacetophenone,with total yield of 20 and 16.3%.All structures of new compounds were confirmed by IR,1H NMR and MS.

  17. Synthesis of derivatives of tetronic acid and pulvinic acid. Total synthesis of norbadione A

    International Nuclear Information System (INIS)

    When vegetables like mushrooms are contaminated by radioactive caesium 137, this radioactive caesium is associated to norbadione A, a natural pigment present in two mushroom species and which can be used as a caesium decorporation agent or maybe as protection agent against ionizing radiations. Within this perspective, this research report describes the biosynthesis and the structure and properties of the norbadione A and of pulvinic acids (physicochemical properties, anti-oxidizing properties). Then, it presents the various tetronic acids (3-acyl-, 3-alkyl-, 3-alkoxy-, 3-aryl-tetronic acids and non 3-substituted tetronic acids), their synthesis path as they are described in the literature, and presents a new synthesis approach using a tandem reaction (with different esters or hydroxy esters) and the synthesis of tetronic acids. The author also proposes a new synthesis way for methyl pulvinates, and finally reports the work on the development of a total synthesis of the norbadione A

  18. A bio-inspired total synthesis of tetrahydrofuran lignans.

    Science.gov (United States)

    Albertson, Anna K F; Lumb, Jean-Philip

    2015-02-01

    Lignan natural products comprise a broad spectrum of biologically active secondary metabolites. Their structural diversity belies a common biosynthesis, which involves regio- and chemoselective oxidative coupling of propenyl phenols. Attempts to replicate this oxidative coupling have revealed significant challenges for controlling selectivity, and these challenges have thus far prevented the development of a unified biomimetic route to compounds of the lignan family. A practical solution is presented that hinges on oxidative ring opening of a diarylcyclobutane to intercept a putative biosynthetic intermediate. The effectiveness of this approach is demonstrated by the first total synthesis of tanegool in 4 steps starting from ferulic acid, as well as a concise synthesis of the prototypical furanolignan pinoresinol.

  19. Total Synthesis of (-)-Spinosyn A via Carbonylative Macrolactonization.

    Science.gov (United States)

    Bai, Yu; Shen, Xingyu; Li, Yong; Dai, Mingji

    2016-08-31

    Spinosyn A (1), a complex natural product featuring a unique 5,6,5,12-fused tetracyclic core structure, is the major component of spinosad, an organic insecticide and an FDA-approved agent used worldwide. Herein, we report an efficient total synthesis of (-)-spinosyn A with 15 steps in the longest linear sequence and 23 steps total from readily available compounds 14 and 23. The synthetic approach features several important catalytic transformations including a chiral amine-catalyzed intramolecular Diels-Alder reaction to afford 22 in excellent diastereoselectivity, a one-step gold-catalyzed propargylic acetate rearrangement to convert 28 to α-iodoenone 31, an unprecedented palladium-catalyzed carbonylative Heck macrolactonization to form the 5,12-fused macrolactone in one step, and a gold-catalyzed Yu glycosylation to install the challenging β-forosamine. This total synthesis is highly convergent and modular, thus offering opportunities to synthesize spinosyn analogues in order to address the emerging cross-resistance problems. PMID:27510806

  20. Asymmetric Synthesis of (3R, 5R)-3-((tert-Butyldimethylsily)oxy)-5-((Z)-2-Bromovinyl)-Tetrahydro-Furan-2-one, an Intermediate for the Synthesis of Fostriecin

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    (3R,5R)-3-((tert-Butyldimethylsily)oxy)-5-((Z)-2-bromovinyl)-tetrahydro-furan-2-one, an intermediate for the synthesis of Fostriecin was achieved by intramolecular asymmetric induction in propene addition of (-)-8-phenylmenthyl glyoxylate followed by inversion of C3-hydroxyl group and Sharpless asymmetric dihydroxylation with simultaneous cyclization to give lactone 5. Then protection of C3-hydroxyl group and oxidation of the C6-primary hydroxyl group which reacted with Wittig reagent to yield the target compound 4.

  1. First total synthesis of four natural prenylated flavonoids

    Institute of Scientific and Technical Information of China (English)

    Jin Hui Yang; Wu Biao Zuo; Dong Dong Guo; Jun Shan Luo; Wen Qian Huang

    2012-01-01

    A facile approach for the first total synthesis of prenylated flavonoids,(±)-abyssinone-Ⅵ-4-O-methyl ether 1,(±)-abyssinone-Ⅳ-4'-O-methyl ether 2,(±)-abyssinone-Ⅴ-4'-O-methyl ether 3 and (±)-sigmoidin E 4 has been described.The key intermediate 4-hydroxy-3,5-di-(3-methylbut-2-enyl)benzaldehyde 6 was also first synthesized that features regioselective prenylation of 4-hydroxybenzaldehyde and crystallizing with petroleum ether from the reaction mixture by freeze-out effect.

  2. Total Synthesis and Biological Assessment of Mandelalide A.

    Science.gov (United States)

    Brütsch, Tobias Michael; Bucher, Pascal; Altmann, Karl-Heinz

    2016-01-22

    A new convergent total synthesis of the marine macrolide mandelalide A (1) has been developed that is based on macrocyclic ring closure by a Shiina-type macrolactonization and the construction of the requisite precursor seco acid by a highly efficient Sonogashira cross-coupling reaction between two fragments of comparable complexity. Key steps in the elaboration of the acid building block were the enantioselective, catalytic addition of a protected acetylene to crotonaldehyde and the construction of the tetrahydropyran unit that is embedded in the macrocycle by means of an acid-catalyzed Prins reaction. The synthesis of the alcohol fragment features the formation of the trisubstituted tetrahydrofuran ring through an acetal cleavage/epoxide opening cascade reaction and a rarely used radical alkynylation of a primary alkyl iodide. Intriguingly, the dihydroxylation of a terminal double bond as part of the synthesis of this building block gave the same major product for both the α- and β-AD-mix reagents, albeit with moderate or low selectivity. Synthetic mandelalide A (1) was a potent proliferation inhibitor of A549, HT460, and H1299 human lung cancer cells in vitro, but not of SK-N-SH neuroblastoma cells. However, in no case did we observe complete cell kill even at the highest compound concentration tested (5 μm). PMID:26639765

  3. Ring-Contraction Strategy for the Practical, Scalable, Catalytic Asymmetric Synthesis of Versatile γ-Quaternary Acylcyclopentenes

    KAUST Repository

    Hong, Allen Y.

    2011-02-24

    Contraction action! A simple protocol for the catalytic asymmetric synthesis of highly functionalized γ-quaternary acylcyclopentenes (see schematic) in up to 91 % overall yield and 92 % ee has been developed. The reaction sequence employs a palladium-catalyzed enantioselective alkylation reaction and exploits the unusual stability of β-hydroxy cycloheptanones to achieve a general and robust method for performing two-carbon ring contractions.

  4. Catalytic asymmetric synthesis of spirocyclic azlactones by a double Michael-addition approach.

    Science.gov (United States)

    Weber, Manuel; Frey, Wolfgang; Peters, René

    2013-06-17

    Spirocyclic azlactones are shown to be useful precursors of cyclic quaternary amino acids, such as the constrained cyclohexane analogues of phenylalanine. These compounds are of interest as building blocks for the synthesis of artificial peptide analogues with controlled folds in the peptide backbone. They were prepared in the present study by a step- and atom-economic catalytic asymmetric tandem approach, requiring two steps starting from N-benzoyl glycine and divinylketones. The key of this protocol is the enantioselective formation of the azlactone spirocycles, which involves a PdII-catalyzed double 1,4-addition of an in situ generated azlactone intermediate to the dienone (a formal [5+1] cycloaddition). As the catalyst, a planar chiral ferrocene bispalladacycle was used. Mechanistic studies suggest a monometallic reaction pathway. Although the diastereoselectivity was found to be moderate, the enantioselectivity is usually high for the formation of the azlactone spirocycles, which contain up to three contiguous stereocenters. Spectroscopic studies have shown that the spirocycles often prefer a twist over a chair conformation of the cyclohexanone moiety. PMID:23613333

  5. Totally asymmetric simple exclusion process with a time-dependent boundary: interaction between vehicles and pedestrians at intersections

    CERN Document Server

    Ito, Hidetaka

    2014-01-01

    Interaction between vehicles and pedestrians is seen in many areas such as crosswalks and intersections. In this paper, we study a totally asymmetric simple exclusion process with a bottleneck at a boundary caused by an interaction. Due to the time-dependent effect originating from the speed of pedestrians, the flow of the model varies even if the average hopping probability at the last site is the same. We analyze the phenomenon by using two types of approximations: (2+1)-cluster approximation and isolated rarefaction wave approximation. The approximate results capture intriguing features of the model. Moreover, we discuss the situation where vehicles turn right at the intersection by adding a traffic light at the boundary condition. The result suggests that pedestrian scrambles are valid to eliminate traffic congestion in the right turn lane.

  6. A new convenient asymmetric approach to herbarumin Ⅲ

    Institute of Scientific and Technical Information of China (English)

    Xue Song Chen; Shi Jun Da; Li Hong Yang; Bo Yan Xu; Zhi Xiang Xie; Ying Li

    2007-01-01

    The asymmetric total synthesis of herbarumin Ⅲ 3, a naturally occurred phytotoxin, along with 8-epi-herbarumin Ⅲ 22, was succeeded in 12 steps from n-butyraldehyde based on Brown's asymmetric allylation, taking modified Julia olefination and Yamaguchi's macro-lactonization as key steps.

  7. Cobalt-catalyzed diastereoselective synthesis of C-furanosides. Total synthesis of (-)-isoaltholactone.

    Science.gov (United States)

    Nicolas, Lionel; Izquierdo, Eva; Angibaud, Patrick; Stansfield, Ian; Meerpoel, Lieven; Reymond, Sébastien; Cossy, Janine

    2013-12-01

    An array of C-aryl and C-vinyl furanosides were prepared in good yields and diastereoselectivities from C-halogeno furanosides either with aryl Grignard or with vinyl Grignard using the convenient Co(acac)3/TMEDA catalytic system. This method is illustrated by the total synthesis of the (-)-isoaltholactone. PMID:24127819

  8. Concise and Straightforward Asymmetric Synthesis of a Cyclic Natural Hydroxy-Amino Acid

    Directory of Open Access Journals (Sweden)

    Mario J. Simirgiotis

    2014-11-01

    Full Text Available An enantioselective total synthesis of the natural amino acid (2S,4R,5R-4,5-di-hydroxy-pipecolic acid starting from D-glucoheptono-1, 4-lactone is presented. The best sequence employed as a key step the intramolecular nucleophilic displacement by an amino function of a 6-O-p-toluene-sulphonyl derivative of a methyl D-arabino-hexonate and involved only 12 steps with an overall yield of 19%. The structures of the compounds synthesized were elucidated on the basis of comprehensive spectroscopic (NMR and MS and computational analysis.

  9. Phase-plane analysis of the totally asymmetric simple exclusion process with binding kinetics and switching between antiparallel lanes

    Science.gov (United States)

    Kuan, Hui-Shun; Betterton, Meredith D.

    2016-01-01

    Motor protein motion on biopolymers can be described by models related to the totally asymmetric simple exclusion process (TASEP). Inspired by experiments on the motion of kinesin-4 motors on antiparallel microtubule overlaps, we analyze a model incorporating the TASEP on two antiparallel lanes with binding kinetics and lane switching. We determine the steady-state motor density profiles using phase-plane analysis of the steady-state mean field equations and kinetic Monte Carlo simulations. We focus on the density-density phase plane, where we find an analytic solution to the mean field model. By studying the phase-space flows, we determine the model’s fixed points and their changes with parameters. Phases previously identified for the single-lane model occur for low switching rate between lanes. We predict a multiple coexistence phase due to additional fixed points that appear as the switching rate increases: switching moves motors from the higher-density to the lower-density lane, causing local jamming and creating multiple domain walls. We determine the phase diagram of the model for both symmetric and general boundary conditions. PMID:27627345

  10. Phase-plane analysis of the totally asymmetric simple exclusion process with binding kinetics and switching between antiparallel lanes

    Science.gov (United States)

    Kuan, Hui-Shun; Betterton, Meredith D.

    2016-08-01

    Motor protein motion on biopolymers can be described by models related to the totally asymmetric simple exclusion process (TASEP). Inspired by experiments on the motion of kinesin-4 motors on antiparallel microtubule overlaps, we analyze a model incorporating the TASEP on two antiparallel lanes with binding kinetics and lane switching. We determine the steady-state motor density profiles using phase-plane analysis of the steady-state mean field equations and kinetic Monte Carlo simulations. We focus on the density-density phase plane, where we find an analytic solution to the mean field model. By studying the phase-space flows, we determine the model's fixed points and their changes with parameters. Phases previously identified for the single-lane model occur for low switching rate between lanes. We predict a multiple coexistence phase due to additional fixed points that appear as the switching rate increases: switching moves motors from the higher-density to the lower-density lane, causing local jamming and creating multiple domain walls. We determine the phase diagram of the model for both symmetric and general boundary conditions.

  11. Phase-plane analysis of the totally asymmetric simple exclusion process with binding kinetics and switching between antiparallel lanes

    CERN Document Server

    Kuan, Hui-Shun

    2016-01-01

    Motor protein motion on biopolymers can be described by models related to the totally asymmetric simple exclusion process (TASEP). Inspired by experiments on the motion of kinesin-4 motors on antiparallel microtubule overlaps, we analyze a model incorporating the TASEP on two antiparallel lanes with binding kinetics and lane switching. We determine the steady-state motor density profiles using phase plane analysis of the steady-state mean field equations and kinetic Monte Carlo simulations. We focus on the the density-density phase plane, where we find an analytic solution to the mean-field model. By studying the phase space flows, we determine the model's fixed points and their changes with parameters. Phases previously identified for the single-lane model occur for low switching rate between lanes. We predict a new multiple coexistence phase due to additional fixed points that appear as the switching rate increases: switching moves motors from the higher-density to the lower-density lane, causing local jamm...

  12. Highly enantioselective and efficient synthesis of flavanones including pinostrobin through the rhodium-catalyzed asymmetric 1,4-addition.

    Science.gov (United States)

    Korenaga, Toshinobu; Hayashi, Keigo; Akaki, Yusuke; Maenishi, Ryota; Sakai, Takashi

    2011-04-15

    An efficient synthesis of bioactive chiral flavanones (1) was achieved through the Rh-catalyzed asymmetric 1,4-addition of arylboronic acid to chromone. The reaction in toluene proceeded smoothly at room temperature in the presence of 0.5% Rh catalyst with electron-poor chiral diphosphine MeO-F(12)-BIPHEP. In this reaction, the 1,2-addition to (S)-1 frequently occurred to yield (2S,4R)-2,4-diaryl-4-chromanol as a byproduct, which could be reduced by changing the reaction solvent to CH(2)Cl(2) to deactivate the Rh catalyst (3% required). PMID:21413690

  13. Synthesis and application of chiral N,N′-dialkylated cyclohexanediamine for asymmetric hydrogenation of aryl ketones

    Institute of Scientific and Technical Information of China (English)

    Meng Lin Ma; Chuan Hong Ren; Ya Jing Lv; Hua Chen; Xian Jun Li

    2011-01-01

    Chiral N,N′-dialkylated cyclohexanediamine derived ligands have been synthesized and used in the asymmetric hydrogenation of aryl ketones. Optically active alcohols with up to 90% enantiomeric excess were obtained in high yields.

  14. Asymmetric synthesis of pedamide using I2-induced heterocyclization to construct the skeleton

    Institute of Scientific and Technical Information of China (English)

    De Gang Liu; Ji Jun Xue; Zhi Xiang Xie; Li Ping Wei; Hua Bing Zhang; Ying Li

    2009-01-01

    An alternative approach to synthesize pedamide, a key building block of pederin was described. Iodine-induced asymmetric heterocyclization was used as the key step to construct the skeleton, a tetrahydropyran ring with three chiral centers. Brown's asymmetric allylation and Lewis acid-mediated allylation were investigated to introduce chains and chiral alcohols. Sharpless dihydroxylation decorated the side chain. And high optically pure target was obtained by removing the epimers formed in these reactions on column chromatography.

  15. Total synthesis of discodermolide: optimization of the effective synthetic route.

    Science.gov (United States)

    de Lemos, Elsa; Porée, François-Hugues; Bourin, Arnaud; Barbion, Julien; Agouridas, Evangelos; Lannou, Marie-Isabelle; Commerçon, Alain; Betzer, Jean-François; Pancrazi, Ange; Ardisson, Janick

    2008-01-01

    An efficient and modulable total synthesis of discodermolide (DDM), a unique marine anticancer polyketide is described including related alternative synthetic approaches. Particularly notable is the repeated application of a crotyltitanation reaction to yield homoallylic (Z)-O-ene-carbamate alcohols with excellent selectivity. Advantage was taken of this reaction not only for the stereocontrolled building of the syn-anti methyl-hydroxy-methyl triads of DDM, but also for the direct construction of the terminal (Z)-diene. Of particular interest is also the installation of the C13=C14 (Z)-double bond through a highly selective dyotropic rearrangement. The preparation of the middle C8-C14 fragment in two sequential stages and its coupling to the C1-C7 moiety was a real challenge and required careful optimization. Several synthetic routes were explored to allow high and reliable yields. Due to the flexibility and robust character of this approach, it might enable a systematic structural variation of DDM and, therefore, the elaboration and exploration of novel discodermolide structural analogues.

  16. Total Synthesis of Natural Products Using Hypervalent Iodine Reagents

    Science.gov (United States)

    Maertens, Gaetan; L'homme, Chloe; Canesi, Sylvain

    2014-12-01

    We present a review of natural product syntheses accomplished in our laboratory during the last five years. Each synthetic route features a phenol dearomatization promoted by an environmentally benign hypervalent iodine reagent. The dearomatizations demonstrate the “aromatic ring umpolung” concept, and involve stereoselective remodeling of the inert unsaturations of a phenol into a highly functionalized key intermediate that may contain a quaternary carbon center and a prochiral dienone system. Several new oxidative strategies were employed, including transpositions (1,3-alkyl shift and Prins-pinacol), a polycyclization, an ipso rearrangement, and direct nucleophilic additions at the phenol para position. Several alkaloids, heterocyclic compounds, and a polycyclic core have been achieved, including sceletenone (a serotonin reuptake inhibitor), acetylaspidoalbidine (an antitumor agent), fortucine (antiviral and antitumor), erysotramidine (curare-like effect), platensimycin (an antibiotic), and the main core of a kaurane diterpene (immunosuppressive agent and stimulator of apoptosis). These concise and in some cases enantioselective syntheses effectively demonstrate the importance of hypervalent iodine reagents in the total synthesis of bioactive natural products.

  17. Total Synthesis of Natural Products Using Hypervalent Iodine Reagents

    Directory of Open Access Journals (Sweden)

    Gaetan eMaertens

    2015-01-01

    Full Text Available We present a review of natural product syntheses accomplished in our laboratory during the last five years. Each synthetic route features a phenol dearomatization promoted by an environmentally benign hypervalent iodine reagent. The dearomatizations demonstrate the aromatic ring umpolung concept, and involve stereoselective remodeling of the inert unsaturations of a phenol into a highly functionalized key intermediate that may contain a quaternary carbon center and a prochiral dienone system. Several new oxidative strategies were employed, including transpositions (1,3-alkyl shift and Prins-pinacol, a polycyclization, an ipso rearrangement, and direct nucleophilic additions at the phenol para position. Several alkaloids, heterocyclic compounds, and a polycyclic core have been achieved, including sceletenone (a serotonin reuptake inhibitor, acetylaspidoalbidine (an antitumor agent, fortucine (antiviral and antitumor, erysotramidine (curare-like effect, platensimycin (an antibiotic, and the main core of a kaurane diterpene (immunosuppressive agent and stimulator of apoptosis. These concise and in some cases enantioselective syntheses effectively demonstrate the importance of hypervalent iodine reagents in the total synthesis of bioactive natural products.

  18. First total synthesis and stereochemical revision of laxaphycin B and its extension to lyngbyacyclamide A.

    Science.gov (United States)

    Boyaud, France; Mahiout, Zahia; Lenoir, Christine; Tang, Shoubin; Wdzieczak-Bakala, Joanna; Witczak, Anne; Bonnard, Isabelle; Banaigs, Bernard; Ye, Tao; Inguimbert, Nicolas

    2013-08-01

    The first total synthesis of laxaphycin B was accomplished through stepwise automated Solid Phase Peptide Synthesis (SPPS), leading to the structural revision of its stereochemistry especially with regard to the configuration of one of the two 3-hydroxyleucines of this cyclic dodecapeptide of marine origin. The analogous Lyngbyacyclamide A was obtained by an extension of this synthesis.

  19. Asymmetric reactions in continuous flow

    Directory of Open Access Journals (Sweden)

    Xiao Yin Mak

    2009-04-01

    Full Text Available An overview of asymmetric synthesis in continuous flow and microreactors is presented in this review. Applications of homogeneous and heterogeneous asymmetric catalysis as well as biocatalysis in flow are discussed.

  20. The transition probability and the probability for the left-most particle's position of the q-totally asymmetric zero range process

    Energy Technology Data Exchange (ETDEWEB)

    Korhonen, Marko [Department of Mathematics and Statistics, University of Helsinki, FIN-00014 (Finland); Lee, Eunghyun [Centre de Recherches Mathématiques (CRM), Université de Montréal, Quebec H3C 3J7 (Canada)

    2014-01-15

    We treat the N-particle zero range process whose jumping rates satisfy a certain condition. This condition is required to use the Bethe ansatz and the resulting model is the q-boson model by Sasamoto and Wadati [“Exact results for one-dimensional totally asymmetric diffusion models,” J. Phys. A 31, 6057–6071 (1998)] or the q-totally asymmetric zero range process (TAZRP) by Borodin and Corwin [“Macdonald processes,” Probab. Theory Relat. Fields (to be published)]. We find the explicit formula of the transition probability of the q-TAZRP via the Bethe ansatz. By using the transition probability we find the probability distribution of the left-most particle's position at time t. To find the probability for the left-most particle's position we find a new identity corresponding to identity for the asymmetric simple exclusion process by Tracy and Widom [“Integral formulas for the asymmetric simple exclusion process,” Commun. Math. Phys. 279, 815–844 (2008)]. For the initial state that all particles occupy a single site, the probability distribution of the left-most particle's position at time t is represented by the contour integral of a determinant.

  1. The transition probability and the probability for the left-most particle's position of the q-totally asymmetric zero range process

    International Nuclear Information System (INIS)

    We treat the N-particle zero range process whose jumping rates satisfy a certain condition. This condition is required to use the Bethe ansatz and the resulting model is the q-boson model by Sasamoto and Wadati [“Exact results for one-dimensional totally asymmetric diffusion models,” J. Phys. A 31, 6057–6071 (1998)] or the q-totally asymmetric zero range process (TAZRP) by Borodin and Corwin [“Macdonald processes,” Probab. Theory Relat. Fields (to be published)]. We find the explicit formula of the transition probability of the q-TAZRP via the Bethe ansatz. By using the transition probability we find the probability distribution of the left-most particle's position at time t. To find the probability for the left-most particle's position we find a new identity corresponding to identity for the asymmetric simple exclusion process by Tracy and Widom [“Integral formulas for the asymmetric simple exclusion process,” Commun. Math. Phys. 279, 815–844 (2008)]. For the initial state that all particles occupy a single site, the probability distribution of the left-most particle's position at time t is represented by the contour integral of a determinant

  2. Asymmetric total synthesis of (-)-jorunnamycins A and C and (-)-jorumycin from L-tyrosine.

    Science.gov (United States)

    Chen, Ruijiao; Liu, Hao; Chen, Xiaochuan

    2013-09-27

    Three renieramycin-type antitumor alkaloids, (-)-jorunnamycins A (1) and C (2) and (-)-jorumycin (3), have been synthesized by a new convergent approach, which features a highly regio- and stereoselective Pictet-Spengler cyclization to couple the isoquinoline and the trisubstituted phenylalaninol partners. This synthetic strategy opens an economical access to these important antitumor alkaloids with high yields: (-)-jorunnamycin A, as a common precursor to other renieramycin-type alkaloids and their analogues, is obtained with 18.1% overall yield from l-tyrosine. PMID:24070054

  3. Recent approaches towards the asymmetric synthesis of α,α-disubstituted α-amino acids

    DEFF Research Database (Denmark)

    Vogt, Henning; Brase, S.

    2007-01-01

    The class of alpha,alpha-disubstituted alpha-amino acids has gained considerable attention in the past decades and continues doing so. The ongoing interest in biological and chemical properties of the substance class has inspired the development of many new methodologies for their asymmetric...

  4. Synthesis of Versatile Building Blocks through Asymmetric Hydrogenation of Functionalized Itaconic Acid Mono-Esters

    NARCIS (Netherlands)

    Hekking, Koen F.W.; Lefort, Laurent; Vries, André H.M. de; Delft, Floris L. van; Schoemaker, Hans E.; Vries, Johannes G. de; Rutjes, Floris P.J.T.

    2008-01-01

    The rhodium-catalyzed asymmetric hydrogenation of several β-substituted itaconic acid mono-esters, using a library of monodentate phosphoramidite and phosphite ligands is described. Two β-alkyl-substituted substrates were readily hydrogenated by the rhodium complex Rh(COD)2BF4 in combination with (S

  5. Asymmetric synthesis of 3-butylphthalide using isomannide and isosorbide as chiral auxiliaries

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A new approach for asymmetric syntheses of (S) and (R)-3-n-butylphthalide (NBP) is presented. The diastereoselective addition of dibutylzinic to aromatic aldehyde 10 or 11 generated from isomannide- or isosorbide-derived chiral auxiliary afforded S-NBP or R-NBP in high optical yields.

  6. Synthesis of 1-Substituted Isoquinolines by Heterocyclization of TosMIC Derivatives: Total Synthesis of Cassiarin A.

    Science.gov (United States)

    Gutiérrez, Sara; Coppola, Anna; Sucunza, David; Burgos, Carolina; Vaquero, Juan J

    2016-07-15

    A new method for the synthesis of 1-substituted isoquinolines by a heterocyclization that involves α-benzyl TosMIC derivatives and different electrophiles has been developed. This methodology has been successfully applied to a total synthesis of cassiarin A, an alkaloid with potent antiplasmodial activity against Plasmodium falciparum. PMID:27351205

  7. The CP molecule labyrinth: a paradigm of how endeavors in total synthesis lead to discoveries and inventions in organic synthesis.

    Science.gov (United States)

    Nicolaou, K C; Baran, Phil S

    2002-08-01

    Imagine an artist carving a sculpture from a marble slab and finding gold nuggets in the process. This thought is not a far-fetched description of the work of a synthetic chemist pursuing the total synthesis of a natural product. At the end of the day, he or she will be judged by the artistry of the final work and the weight of the gold discovered in the process. However, as colorful as this description of total synthesis may be, it does not entirely capture the essence of the endeavor, for there is much more to be told, especially with regard to the contrast of frustrating failures and exhilarating moments of discovery. To fully appreciate the often Herculean nature of the task and the rewards that accompany it, one must sense the details of the enterprise behind the scenes. A more vivid description of total synthesis as a struggle against a tough opponent is perhaps appropriate to dramatize these elements of the experience. In this article we describe one such endeavor of total synthesis which, in addition to reaching the target molecule, resulted in a wealth of new synthetic strategies and technologies for chemical synthesis. The total synthesis of the CP molecules is compared to Theseus' most celebrated athlos (Greek for exploit, accomplishment): the conquest of the dreaded Minotaur, which he accomplished through brilliance, skill, and bravery having traversed the famous labyrinth with the help of Ariadne. This story from Greek mythology comes alive in modern synthetic expeditions toward natural products as exemplified by the total synthesis of the CP molecules which serve as a paradigm for modern total synthesis endeavors, where the objectives are discovery and invention in the broader sense of organic synthesis. PMID:12203464

  8. Total synthesis and evaluation of [18F]MHMZ

    DEFF Research Database (Denmark)

    Herth, Matthias M; Debus, Fabian; Piel, Markus;

    2008-01-01

    Radiochemical labeling of MDL 105725 using the secondary labeling precursor 2-[(18)F]fluoroethyltosylate ([(18)F]FETos) was carried out in yields of approximately 90% synthesizing [(18)F]MHMZ in a specific activity of approximately 50MBq/nmol with a starting activity of approximately 3GBq. Overall...... radiochemical yield including [(18)F]FETos synthon synthesis, [(18)F]fluoroalkylation and preparing the injectable [(18)F]MHMZ solution was 42% within a synthesis time of approximately 100 min. The novel compound showed excellent specific binding to the 5-HT(2A) receptor (K(i)=9.0 nM) in vitro and promising in...

  9. Synthesis of solution-phase phosphoramidite and phosphite ligand libraries and their in situ screening in the rhodium-catalyzed asymmetric addition of arylboronic acids

    NARCIS (Netherlands)

    Jagt, Richard B. C.; Toullec, Patrick Y.; Schudde, Ebe P.; de Vries, Johannes G.; Feringa, Ben L.; Minnaard, Adriaan J.

    2007-01-01

    Herein, we report the automated parallel synthesis of solution-phase libraries of phosphoramidite ligands for the development of enantioselective catalysts. The ligand libraries are screened in situ in the asymmetric rhodium-catalyzed addition of arylboronic acids to aldehydes and imines. It is show

  10. A Concise Total Synthesis of S-(+)-Tylophorine

    Institute of Scientific and Technical Information of China (English)

    JIN,Zhong; WANG,Qing-Min; LI,Hao; LIU,Yu-Xiu; LI,Shi-Pu; HUANG,Run-Qiu

    2004-01-01

    @@ Phenanthroindolizidine alkaloids, which exhibit extensively biological properties, are widely present at various plants of the Asclepiadaceae family.[1] The significantly biological importance of these natural products has attracted considerable synthetic efforts.[2] We herein report an efficiently asyinmetric synthesis of S-(+)-tylophorine (1), as a typically representative alkaloids.

  11. The Catalytic Enantioselective Total Synthesis of (+)‐Liphagal

    DEFF Research Database (Denmark)

    Day, Joshua J.; McFadden, Ryan M.; Virgil, Scott C.;

    2011-01-01

    catalysis, and an intramolecular aryne capture cyclization reaction. Pivotal to the successful completion of the synthesis was a sequence involving ring expansion from a [6-5-4] tricycle to a [6-7] bicyclic core followed by stereoselective hydrogenation of a sterically occluded tri-substituted olefin...

  12. The total chemical synthesis of polymer/graphene nanocomposite films.

    Science.gov (United States)

    Salvatierra, Rodrigo V; Cava, Carlos E; Roman, Lucimara S; Oliveira, Marcela M; Zarbin, Aldo J G

    2016-01-28

    A versatile and room temperature synthesis of thin films of polymer/graphene is reported. Drastically differing from other methods, not only the polymer but also the graphene are completely built from their simplest monomers (thiophene and benzene) in a one-pot polymerization reaction at a liquid-liquid interface. The materials were characterized and electronic properties are presented. PMID:26658554

  13. Asymmetric Inducing Synthesis of Optically Active Tetrahedral Cluster Containing SMCoW Core

    Institute of Scientific and Technical Information of China (English)

    ZHAO,Quan-Yi(赵全义); ZHANG,Yu-Hua(张玉华); HU,Bin(胡斌); ZHANG,Wei-Qiang(张伟强); ZHU,Bao-Hua(朱保华); YIN,Yuan-Qi(殷元骐); XIA,Chun-Gu(夏春谷)

    2004-01-01

    The chiral clusters (μ3-S)MCoW(CO)8[η5-CsH4C(O)OCH3] [M=Ru (2), Fe (3)] were synthesized by asymmetric induction of N-benzylcinchonium chloride as phase-transfer catalyst (PTC). The most suitable amount of PTC is 70 mol%. Cluster 3 was determined by single crystal X-ray diffraction analysis. The best ee of the chiral cluster is over 20%.

  14. Design,Synthesis of Chiral Ketone and Application in Asymmetric Epoxidation

    Institute of Scientific and Technical Information of China (English)

    She Xue-gong; Tian Hong-qi; Shi Yi-an

    2004-01-01

    A class of chiral ketone was synthesized for asymmetric epoxidation. High ee values have been obtained for a number of cis olefin and trans olefin. The epoxidation was stereospecific with no isomerizatiom observed in the epoxidation of acyclic system. Encourageingly high ee value has also been obtained for a number of terminal olefins. Mechanistic studies show that electronic interactions play an important role in the stereodifferentiation.

  15. Asymmetric Synthesis and Absolute Configuration Assignment of a New Type of Bedaquiline Analogue

    OpenAIRE

    Chang-Jiang Qiao; Xiao-Kui Wang; Fei Xie; Wu Zhong; Song Li

    2015-01-01

    Bedaquiline is the first FDA-approved new chemical entity to fight multidrug-resistant tuberculosis in the last forty years. Our group replaced the quinoline ring with a naphthalene ring, leading to a new type of triarylbutanol skeleton. An asymmetric synthetic route was established for our bedaquiline analogues, and the goal of assigning their absolute configurations was achieved by comparison of experimental and calculated electronic circular dichroism spectra, and was confirmed by the comb...

  16. Synthesis of Main-Chain Chiral Quaternary Ammonium Polymers for Asymmetric Catalysis Using Quaternization Polymerization

    Directory of Open Access Journals (Sweden)

    Md. Masud Parvez

    2012-06-01

    Full Text Available Main-chain chiral quaternary ammonium polymers were successfully synthesized by the quaternization polymerization of cinchonidine dimer with dihalides. The polymerization occurred smoothly under optimized conditions to give novel type of main-chain chiral quaternary ammonium polymers. The catalytic activity of the polymeric chiral organocatalysts was investigated on the asymmetric benzylation of N-(diphenylmethylideneglycine tert-butyl ester.

  17. Chiral PEPPSI Complexes: Synthesis, Characterization, and Application in Asymmetric Suzuki–Miyaura Coupling Reactions

    KAUST Repository

    Benhamou, Laure

    2014-01-13

    PEPPSI complexes incorporating chiral N-heterocyclic carbene (NHC) ligands based on 2,2-dimethyl-1-(o-substituted aryl)propan-1-amines were synthesized. Two complexes, with one saturated and one unsaturated NHC ligand, were structurally characterized. The chiral PEPPSI complexes were used in asymmetric Suzuki-Miyaura reactions, giving atropisomeric biaryl products in modest to good enantiomeric ratios. © 2013 American Chemical Society.

  18. Asymmetric silica encapsulation toward colloidal Janus nanoparticles: a concave nanoreactor for template-synthesis of an electocatalytic hollow Pt nanodendrite

    Science.gov (United States)

    Koo, Jung Hun; Kim, Daun; Kim, Jin Goo; Jeong, Hwakyeung; Kim, Jongwon; Lee, In Su

    2016-07-01

    A novel reverse microemulsion strategy was developed to asymmetrically encapsulate metal-oxide nanoparticles in silica by exploiting the self-catalytic growth of aminosilane-containing silica at a single surface site. This strategy produced various colloidal Janus nanoparticles, including Au/Fe3O4@asy-SiO2, which were converted to an Au-containing silica nanosphere, Au@con-SiO2, by reductive Fe3O4 dissolution. The use of Au@con-SiO2 as a metal-growing nanoreactor allowed the templated synthesis of various noble-metal nanocrystals, including a hollow dendritic Pt nanoshell which exhibits significantly better electrocatalytic activities for the oxygen reduction reaction than commercial Pt/C catalysts.A novel reverse microemulsion strategy was developed to asymmetrically encapsulate metal-oxide nanoparticles in silica by exploiting the self-catalytic growth of aminosilane-containing silica at a single surface site. This strategy produced various colloidal Janus nanoparticles, including Au/Fe3O4@asy-SiO2, which were converted to an Au-containing silica nanosphere, Au@con-SiO2, by reductive Fe3O4 dissolution. The use of Au@con-SiO2 as a metal-growing nanoreactor allowed the templated synthesis of various noble-metal nanocrystals, including a hollow dendritic Pt nanoshell which exhibits significantly better electrocatalytic activities for the oxygen reduction reaction than commercial Pt/C catalysts. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr03557d

  19. Lepadiformine: a case study of the value of total synthesis in natural product structure elucidation.

    Science.gov (United States)

    Weinreb, Steven M

    2003-01-01

    Since the emergence of routine X-ray crystallography and high-field FT NMR in the mid-twentieth century, the importance of total synthesis in structure elucidation has become underappreciated by most organic chemists. However, the limitations and fallibility of spectral methodology has recently been highlighted by the mischaracterization of a number of complex natural products, the correct structures of which were all ultimately assigned by total synthesis. This account describes how total synthesis was not only instrumental in disproving the erroneously assigned structure of the marine alkaloid, lepadiformine, but also was also pivotal in establishing the correct structure and absolute configuration.

  20. Progress Toward the Total Synthesis of Vinigrol and Hibarimicin B

    OpenAIRE

    Milgram, Benjamin Charles

    2013-01-01

    Vinigrol is a structurally unique diterpenoid natural product featuring a tricyclo[4.4.4.0.4a,8a]tetradecene carbon skeleton containing eight contiguous stereocenters and a challenging oxygenation pattern. Vinigrol has been demonstrated to possess a wide array of biological activities including tumor necrosis factor (TNF) antagonism, antihypertensive activity, and platelet aggregation inhibitory activity. Our first-generation plan for the synthesis of vinigrol utilized a cascade reaction sequ...

  1. Total Synthesis of Nominal Cyclocinamide B and Investigation into the Identity of the Cyclocinamides

    OpenAIRE

    Curzon, Stephanie S.; Garcia, Jessica M.; Konopelski, Joseph P.

    2014-01-01

    The total synthesis of nominal cyclocinamide B, a cyclic peptide marine natural product, is reported together with an isomer of nominal cyclocinamide A. Initial attempts at the synthesis of the title compounds by inclusion of a turn inducer failed. However, direct synthesis succeeded in formation of the 14-membered cyclic peptide structure. Comparison of the data from all synthetic cyclocinamide A and B compounds with those of the natural products leads to the conclusion that the two natural ...

  2. Enantioselective total synthesis of (+)-Lingzhiol via tandem semipinacol rearrangement/Friedel-Crafts type cyclization.

    Science.gov (United States)

    Chen, Dong; Xu, Wen-Dan; Liu, Hao-Miao; Li, Ming-Ming; Yan, Yong-Min; Li, Xiao-Nian; Li, Yan; Cheng, Yong-Xian; Qin, Hong-Bo

    2016-06-30

    Enantioselective total synthesis of (+)-Lingzhiol has been achieved. It is the first example of in tandem semipinacol rearrangement reactions, the migrated aryl group further reacting with the carbonyl oxonium electrophile to furnish a polycyclic skeleton. Our synthesis involves 13 steps and proceeds in 6% overall yield. PMID:27321202

  3. Novel Chiral PNNP-Ru Complexes: Synthesis and Application in Asymmetric Transfer Hydrogenation of Ketones

    Institute of Scientific and Technical Information of China (English)

    CHENG Zhi-bo; YU Shen-luan; LI Yan-yun; DONG Zhen-rong; SUN Guo-song; HUANG Ke-lin; GAO Jing-xing

    2011-01-01

    The efficient catalytic systems generated in situ from RuCl2(PPh3)3 and chiral ligands N,N-bis[2-(di-otolylphosphino)-benzyl]cyclohexane-l,2-diamine(2) were employed for asymmetric transfer hydrogenation of aromatic ketones, giving the corresponding optically active alcohols with high activities(up to 99% conversion) and excellent enantioselectivities(up to 96% e.e.) under mild conditions. The chiral ruthenium(Ⅱ) complex (R,R)-3 has been prepared and characterized by NMR and X-ray crystallography.

  4. Catalytic asymmetric synthesis of a tertiary benzylic carbon center via phenol-directed alkene hydrogenation.

    Science.gov (United States)

    Caille, Seb; Crockett, Rich; Ranganathan, Krishnakumar; Wang, Xiang; Woo, Jacqueline C S; Walker, Shawn D

    2011-07-01

    An expeditious synthetic approach to chiral phenol 1, a key building block in the preparation of a series of drug candidates, is reported. The strategy includes a cost-effective and readily scalable route to cyclopentanone 3 from isobutyronitrile (10). The sterically hindered and enolizable ketone 3 was subsequently employed in a challenging Grignard addition mediated by LaCl(3)·2LiCl. A novel preparation of the lanthanide reagent required for this transformation is described. To complete the process, a highly enantioselective hydrogenation step afforded the target (1). The importance of the phenol group to the success of this asymmetric transformation is discussed. PMID:21630712

  5. Asymmetric Synthesis and Absolute Configuration Assignment of a New Type of Bedaquiline Analogue

    Directory of Open Access Journals (Sweden)

    Chang-Jiang Qiao

    2015-12-01

    Full Text Available Bedaquiline is the first FDA-approved new chemical entity to fight multidrug-resistant tuberculosis in the last forty years. Our group replaced the quinoline ring with a naphthalene ring, leading to a new type of triarylbutanol skeleton. An asymmetric synthetic route was established for our bedaquiline analogues, and the goal of assigning their absolute configurations was achieved by comparison of experimental and calculated electronic circular dichroism spectra, and was confirmed by the combined use of circular dichroism and NMR spectroscopy.

  6. Asymmetric Synthesis and Absolute Configuration Assignment of a New Type of Bedaquiline Analogue.

    Science.gov (United States)

    Qiao, Chang-Jiang; Wang, Xiao-Kui; Xie, Fei; Zhong, Wu; Li, Song

    2015-01-01

    Bedaquiline is the first FDA-approved new chemical entity to fight multidrug-resistant tuberculosis in the last forty years. Our group replaced the quinoline ring with a naphthalene ring, leading to a new type of triarylbutanol skeleton. An asymmetric synthetic route was established for our bedaquiline analogues, and the goal of assigning their absolute configurations was achieved by comparison of experimental and calculated electronic circular dichroism spectra, and was confirmed by the combined use of circular dichroism and NMR spectroscopy. PMID:26690407

  7. Flexible and Asymmetric Ligand in Constructing Coordinated Complexes: Synthesis, Crystal Structures and Fluorescent Characterization

    Directory of Open Access Journals (Sweden)

    Jianhua Lin

    2010-12-01

    Full Text Available Flexible and asymmetric ligand L [L = 1-((pyridin-3-ylmethyl-1H-benzotriazole], is used as a basic backbone to construct complicated metal-organic frameworks. Two new polymers, namely, [Ag2(L2(NO32]n (1 and [Ag(L(ClO4]n (2, were synthesized and characterized by X-ray structure analysis and fluorescent spectroscopy. The complex 1 gives an “S” type double helical conformation, whereas complex 2 exhibits a 1D zigzag configuration. Different anions affect the silver coordination geometry and crystal packing topology.

  8. Total synthesis and allelopathic activity of cytosporones A-C

    Energy Technology Data Exchange (ETDEWEB)

    Zamberlam, Charles E.M.; Meza, Alisson; Lima, Denis P. de; Beatriz, Adilson [Centro de Ciencias Exatas e Tecnologia, Universidade Federal de Mato Grosso do Sul, Campo Grande, MS (Brazil); Leite, Carla Braga; Marques, Maria Rita [Centro de Ciencias Biologicas e da Saude, Universidade Federal de Mato Grosso do Sul, Campo Grande, MS (Brazil)

    2012-07-01

    The search for efficient, environmentally friendly herbicides has been the focus of numerous studies on the organic synthesis of compounds isolated from natural sources. Cytosporones, which are phenolic lipids isolated from fungi, exhibit noteworthy biological properties. This paper reports the preparation of cytosporones A-C from the same starting material through a short synthetic route, with good yields. All compounds were tested for allelopathic activity on lettuce (Lactuca sativa L) seeds. Cytosporone A and its methylated precursor showed remarkable allelopathic activity, inhibiting seed germination and plantule growth. (author)

  9. Remarkable Stereoelectronic Effect of the Methylenedioxy Phenyl System in the Total Synthesis of Cephalotaxine

    Institute of Scientific and Technical Information of China (English)

    Hua YANG; Yong Qiang WANG; Wei DongZ. LI

    2005-01-01

    Methylenedioxyphenyl unit displays a significant stereoelectronic effect in some key transformations in the total synthesis of cephalotaxine. The ring-strain of methylenedioxy ring may account for some important facile ring-skeleton rearrangements.

  10. Harnessing Quinone Methides: Total Synthesis of (±)‐Vaticanol A

    DEFF Research Database (Denmark)

    Jepsen, Tue Heesgaard; Thomas, Stephen; Yunqing, lin;

    2014-01-01

    Although quinone methides are often postulated as intermediates in the biosynthesis of many polyphenolic natural products, deploying their power in a laboratory setting to achieve similar bond constructions has sometimes proven challenging. Herein, a total synthesis of the resveratrol trimer...

  11. A carbohydrate approach for the formal total synthesis of (−-aspergillide C

    Directory of Open Access Journals (Sweden)

    Pabbaraja Srihari

    2014-12-01

    Full Text Available An enantioselective formal total synthesis of aspergillide C is accomplished using commercially available tri-O-acetyl-D-galactal employing a Ferrier-type C-glycosylation, utilizing a Trost hydrosilylation and protodesilylation as key reactions.

  12. Some Remarks on Asymmetric Syntheses from Recent Studies

    OpenAIRE

    Baba, Naomichi

    1990-01-01

    Some asymmetric syntheses were presented here and discussed briefly including NADH model reactions, phase transfer-catalyzed asymmetric epoxidation, enantiotopic group-selective hydrolysis of a malonic anhydride with alkoxide anion, intramolecular acid-catalyzed lactonizations, catalytic asymmetric Diels-Alder synthesis, asymmetric aldol condensation, chiral homoallyl alcohol synthesis, asymmetric addition of diethylzinc to aldehyde, kinetic resolution of racemic hydroperoxides and binaphthol...

  13. New Organocatalytic Asymmetric Synthesis of Highly Substituted Chiral 2-Oxospiro-[indole-3,4′- (1′,4′-dihydropyridine] Derivatives

    Directory of Open Access Journals (Sweden)

    Fernando Auria-Luna

    2015-08-01

    Full Text Available Herein, we report our preliminary results concerning the first promising asymmetric synthesis of highly functionalized 2-oxospiro-[indole-3,4′-(1′,4′-dihydropyridine] via the reaction of an enamine with isatylidene malononitrile derivatives in the presence of a chiral base organocatalyst. The moderate, but promising, enantioselectivity observed (30%–58% ee (enantiomeric excess opens the door to a new area of research for the asymmetric construction of these appealing spirooxindole skeletons, whose enantioselective syntheses are still very limited.

  14. Linear and total intersubband transitions in the step-like GaAs/GaAlAs asymmetric quantum well as dependent on intense laser field

    Science.gov (United States)

    Ozturk, Emine

    2015-11-01

    In this study, for a step-like GaAs- Ga_{1-x}AlxAs asymmetric quantum well (AQW) the linear and total intersubband optical absorption coefficients and the refractive index changes are calculated as dependent on the intense laser field (ILF) and the right quantum well (RQW) width. Our results show that the location and the magnitude of all absorption coefficients and refractive index changes depend on ILF and the asymmetric parameter ( d=LR/LL). Also, we showed that both ILF and d provide an important effect on the electronic and optical properties of step-like quantum well, and the changes of the energy levels, the dipole moment matrix elements and the resonant peak values of the absorption coefficients are dependent on the shape of the confinement potential. While for different asymmetric parameters the intersubband absorption spectrum shows blue shift up to the different critical ILF values, this spectrum shows red shift for ILF values greater than certain values. By considering the variation of the energy difference as dependent on the RQW width, for step-like QW the absorption spectrum shows blue or red shift. Especially, step-like QWs are used for producing terahertz radiation from intersubband transitions and they have more tunable structure parameters (the left (right) quantum well width, LL(LR), and the confinement potential in the left (right) hand side, VL (VR) with respect to other asymmetric QWs (in the present study we used LR=LL/2, LL, 3 L L/2 and V R = 2 V L/3 values). This case provides a new degree of freedom for controlling the optical properties in quantum wells (QWs). In addition, the nonlinear optics underlying the application of the ILF to asymmetric potential heterostructures becomes a subject of present-day interest. In conclusion: i) The electronic and optical properties of the step-like AQW vary by increasing ILF. ii) ILF leads to major modifications on the shape of the confining potential. iii) The position and the size of all absorption

  15. Total Synthesis of Sporolide B and 9-epi-Sporolide B

    OpenAIRE

    Nicolaou, K. C.; Wang, Jianhua; Tang, Yefeng; Botta, Lorenzo

    2010-01-01

    The total synthesis of the structurally unique secondary metabolite sporolide B (1b, Figure 1) is described. The total synthesis of 1b was developed on the basis of preliminary studies that revealed the reactivity of an appropriate o-quinone as a diene system toward a number of indene derivatives as dienophiles, first in intermolecular and thence intramolecular settings. Thus, substrates were devised (37, Scheme 5; 75, Scheme 11) that underwent exquisite intramolecular [4+2] cycloaddition rea...

  16. Stereoselective synthesis of the C1-C13 fragment of (+)-discodermolide using asymmetric allyltitanations.

    Science.gov (United States)

    BouzBouz, Samir; Cossy, Janine

    2003-08-21

    [reaction: see text] The synthesis of the C1-C13 fragment of (+)-discodermolide has been achieved. The configurations of the stereogenic centers have been controlled by enantioselective allyl- and crotyltitanations of aldehydes, and the Z configuration of the olefin at C8-C9 was controlled by a ring-closing metathesis.

  17. Synthesis and biological evaluation of asymmetric gramicidin S analogues containing modified D-phenylalanine residues

    NARCIS (Netherlands)

    van der Knaap, Matthijs; Engels, Eefje; Busscher, Henk J.; Otero, Jose M.; Llamas-Saiz, Antonio L.; van Raaij, Mark J.; Mars-Groenendijk, Roos H.; Noort, Daan; van der Marel, Gijsbert A.; Overkleeft, Herman S.; Overhand, Mark

    2009-01-01

    The synthesis of new analogues of the cationic antimicrobial peptide gramicidin S, having a modified D-phenylalanine residue, their antibacterial properties against several Gram positive and negative strains, as well as their hemolytic activity is reported. (C) 2009 Elsevier Ltd. All rights reserved

  18. Synthesis and biological evaluation of asymmetric gramicidin S analogues containing modified d-phenylalanine residues

    NARCIS (Netherlands)

    Knaap, M. van der; Engels, E.; Busscher, H.J.; Otero, J.M.; Llamas-Saiz, A.L.; Raaij, M.J. van; Mars-Groenendijk, R.H.; Noort, D.; Marel, G.A. van der; Overkleeft, H.S.; Overhand, M.

    2009-01-01

    The synthesis of new analogues of the cationic antimicrobial peptide gramicidin S, having a modified d-phenylalanine residue, their antibacterial properties against several Gram positive and negative strains, as well as their hemolytic activity is reported. © 2009 Elsevier Ltd. All rights reserved.

  19. Synthesis, Characterization and Properties of Asymmetric Methide Anion Based Ionic Liquids Containing Nitrile Groups

    Institute of Scientific and Technical Information of China (English)

    ZOU Ting; LU Liang; LIU Xiu-Li; ZHANG Zhan; WANG Li-Bing; FU Xian-Lei; GAO Guo-Hua; KOU Yuan; HE Ming-Yuan

    2008-01-01

    A series of asymmetric methide anion based ionic liquids containing nitrile groups have been synthesized for the first time using the method of ion-exchange between sodium/potassium methide and various quaternary bro-mide/chloride salts of trimethylamine, triethylamine, tributylamine, N-methylpyrrolidine, and N-methylimidazole. All of the functionalised ionic liquids were characterized by IR, 1H, 13C NMR, MS and elemental analysis. The de-composition temperature of the ionic liquids measured via TGA ranged from 219 to 339 ℃. The functionalised ionic liquid, [Bmim][C(CN)2COCH3], was used as a ligand for Suzuki coupling reaction. The yields of the coupling reaction increased 10%-15% by the addition of the functionalised ionic liquid, [Bmim] [C(CN)2COCH3].

  20. Concise methods for the synthesis of chiral polyoxazolines and their application in asymmetric hydrosilylation

    Directory of Open Access Journals (Sweden)

    Wei Jie Li

    2010-03-01

    Full Text Available Seven polyoxazoline ligands were synthesized in high yield in a one-pot reaction by heating polycarboxylic acids or their esters and chiral β-amino alcohols under reflux with concomitant removal of water or the alcohol produced in the reaction. The method is much simpler and more efficient in comparison to those methods reported in the literature.The compounds were used as chiral ligands in the rhodium-catalyzed asymmetric hydrosilylation of aromatic ketones, and the effects of the linkers and the substituents present on the oxazoline rings on the yield and enantioselectivity investigated. Compound 2 was identified as the best ligand of this family for the hydrosilylation of aromatic ketones.

  1. Large Scale Synthesis of NiCo Layered Double Hydroxides for Superior Asymmetric Electrochemical Capacitor

    Science.gov (United States)

    Li, Ruchun; Hu, Zhaoxia; Shao, Xiaofeng; Cheng, Pengpeng; Li, Shoushou; Yu, Wendan; Lin, Worong; Yuan, Dingsheng

    2016-01-01

    We report a new environmentally-friendly synthetic strategy for large-scale preparation of 16 nm-ultrathin NiCo based layered double hydroxides (LDH). The Ni50Co50-LDH electrode exhibited excellent specific capacitance of 1537 F g-1 at 0.5 A g-1 and 1181 F g-1 even at current density as high as 10 A g-1, which 50% cobalt doped enhances the electrical conductivity and porous and ultrathin structure is helpful with electrolyte diffusion to improve the material utilization. An asymmetric ultracapacitor was assembled with the N-doped graphitic ordered mesoporous carbon as negative electrode and the NiCo LDH as positive electrode. The device achieves a high energy density of 33.7 Wh kg-1 (at power density of 551 W kg-1) with a 1.5 V operating voltage.

  2. Synthesis and characterization of polystyrene coated iron oxide nanoparticles and asymmetric assemblies by phase inversion

    KAUST Repository

    Xie, Yihui

    2014-09-02

    Films with a gradient concentration of magnetic iron oxide nanoparticles are reported, based on a phase inversion membrane process. Nanoparticles with ∼13 nm diameter were prepared by coprecipitation in aqueous solution and stabilized by oleic acid. They were further functionalized by ATRP leading to grafted polystyrene brush. The final nanoparticles of 33 nm diameter were characterized by TGA, FTIR spectroscopy, GPC, transmission electron microscopy, and dynanmic light scattering. Asymmetric porous nanoparticle assemblies were then prepared by solution casting and immersion in water. The nanocomposite film production with functionalized nanoparticles is fast and technically scalable. The morphologies of films were characterized by scanning electron microscopy and atomic force microscopy, demonstrating the presence of sponge-like structures and finger-like cavities when 50 and 13 wt % casting solutions were, respectively, used. The magnetic properties were evaluated using vibrating sample magnetometer.

  3. Synthesis of sulphonated mesoporous phenolic resins and their application in esterification and asymmetric aldol reactions

    Energy Technology Data Exchange (ETDEWEB)

    Muylaert, Ilke [Department of Inorganic and Physical Chemistry, Ghent University, Center for Ordered Materials, Organometallics and Catalysis (COMOC), Krijgslaan 281-S3, 9000 Ghent (Belgium); Verberckmoes, An, E-mail: an.verberckmoes@hogent.be [Department of Inorganic and Physical Chemistry, Ghent University, Center for Ordered Materials, Organometallics and Catalysis (COMOC), Krijgslaan 281-S3, 9000 Ghent (Belgium); Associated Faculty of Applied Engineering Sciences, University College Ghent, Valentin Vaerwyckweg 1, 9000 Ghent (Belgium); Spileers, Jeremy [Associated Faculty of Applied Engineering Sciences, University College Ghent, Valentin Vaerwyckweg 1, 9000 Ghent (Belgium); Demuynck, Anneleen; Peng, Li; De Clippel, Filip; Sels, Bert [Katholieke Universiteit Leuven, Centre for Surface Chemistry and Catalysis (COK), Kasteelpark Arenberg 23, 3001 Heverlee (Belgium); Van Der Voort, Pascal, E-mail: pascal.vandervoort@ugent.be [Department of Inorganic and Physical Chemistry, Ghent University, Center for Ordered Materials, Organometallics and Catalysis (COMOC), Krijgslaan 281-S3, 9000 Ghent (Belgium)

    2013-02-15

    Mesoporous phenolic resins were functionalized with sulphonic acid groups by four different types of sulphonation procedures: (i) direct sulphonation on the aromatic ring, (ii) alkyl sulphonation of the aromatic ring, and functionalizations of the phenolic hydroxyl surface by using an aryl silane, 2-(4-chlorosulphonylphenyl)ethyl trichlorosilane (iii) or a propyl silane, 3-mercaptopropyltrimethoxysilane (iv). The highest acidity loadings were obtained through direct sulphonation with fuming sulphuric acid (1.90 mmol H{sup +} g{sup −1}) or chlorosulphonic acid (1.31 mmol H{sup +} g{sup −1}) and these materials showed the highest conversion (97+ %) in Fischer esterification of acetic acid with propanol. However, the alkyl sulphonic groups, obtained through sulphonation procedure (ii) showed the highest stability in terms of maintenance of their acidity after use in consecutive catalytic runs or leaching treatments. This was demonstrated both through evaluation of the regenerated catalysts in a consecutive esterification run and during a leaching resistance test in aqueous medium. Moreover, the developed sulphonated mesoporous phenolic resins are presented as novel support for the non-covalent immobilization of an L-phenylalanine derived chiral diamine organocatalyst for asymmetric aldol reactions. The immobilization is established by an acid–base interaction between the sulphonic acid group and the amine function. The acidity and in particular the electronic withdrawing environment of the sulphonic acid groups influence enormously the catalytic performance of the non-covalent immobilized chiral diamine catalyst (aromatic > aliphatic). - Highlights: ► Different types of sulphonation procedures for mesoporous phenolic resins. ► Influence of acidity and electronic withdrawing environment. ► Novel support for non-covalent immobilization of chiral diamine catalyst. ► Catalytic performance in esterification and asymmetric aldol condensation. ► Demonstration

  4. Studies directed toward the total synthesis of discodermolide: asymmetric synthesis of the C1-C14 fragment.

    Science.gov (United States)

    Arefolov, Alexander; Panek, James S

    2002-07-11

    [structure: see text] A convergent and stereoselective assembly of the C1-C14 subunit of marine natural product (+)-discodermolide has been completed. The approach employs chiral allylsilane bond construction methodology to establish four of the eight stereogenic centers. Key fragment coupling is achieved via an efficient stereoselective acetate aldol reaction between C1-C6 and C7-C14 subunits.

  5. Asymmetric Desymmetrization via Metal-Free C-F Bond Activation: Synthesis of 3,5-Diaryl-5-fluoromethyloxazolidin-2-ones with Quaternary Carbon Centers.

    Science.gov (United States)

    Tanaka, Junki; Suzuki, Satoru; Tokunaga, Etsuko; Haufe, Günter; Shibata, Norio

    2016-08-01

    We disclose the first asymmetric activation of a non-activated aliphatic C-F bond in which a conceptually new desymmetrization of 1,3-difluorides by silicon-induced selective C-F bond scission is a key step. The combination of a cinchona alkaloid based chiral ammonium bifluoride catalyst and N,O-bis(trimethylsilyl)acetoamide (BSA) as the silicon reagent enabled the efficient catalytic cycle of asymmetric Csp3 -F bond cleavage under mild conditions with high enantioselectivities. The ortho effect of the aryl group at the prostereogenic center is remarkable. This concept was applied for the asymmetric synthesis of promising agrochemical compounds, 3,5-diaryl-5-fluoromethyloxazolidin-2-ones bearing a quaternary carbon center.

  6. Total synthesis of amiclenomycin, an inhibitor of biotin biosynthesis.

    Science.gov (United States)

    Mann, Stéphane; Carillon, Sophie; Breyne, Olivier; Marquet, Andrée

    2002-01-18

    We describe the first synthesis of amiclenomycin, a natural product that has been found to inhibit biotin biosynthesis and, as a consequence, to exhibit antibiotic properties. Structure 1, with a trans relationship between the ring substituents. had previously been proposed for amiclenomycin on the basis of its 1H NMR spectrum. We have prepared the trans and cis isomers 1 and 2 by unequivocal routes and we conclude that the natural product is in fact the cis isomer 2. The properly substituted cyclohexadienyl rings were constructed first. A cycloaddition reaction between 1,2-di(phenylsulfonyl)ethylene and the N-allyloxycarbonyl diene 13, followed by reductive elimination of the phenylsulfinyl groups, gave the cis isomer 15. To obtain the trans isomer, the O-trimethylsilyl diene was used to give the cis hydroxylated Diels-Alder adduct 33, which was transformed into the corresponding trans amino derivative by means of a Mitsunobu reaction. The L-alpha-amino acid functionality was introduced by means of a Strecker reaction on the aldehydes 16 and 42, followed by enzymatic hydrolysis with immobilised pronase. PMID:11843156

  7. Synthesis of asymmetric supramolecular compounds using a Ni(0) catalysed homo-coupling approach

    NARCIS (Netherlands)

    Cassidy, Lynda; Horn, Sabine; Cleary, Laura; Halpin, Yvonne; Browne, Wesley R.; Vos, Johannes G.

    2009-01-01

    The synthesis and characterisation of a series of dinuclear ruthenium and osmium polypyridyl metal complexes based on the bridging ligands [5-(5'-bipyridin-2',2 ''-yl)-3-(pyridin-2-yl)]-1,2,4-triazole (Hpytr-bipy), 2,2 ''-bis(pyridin-2 '' yl)-5,5 ''-bis(pyridin-3 ''-yl) (bipy-bipy) and 5,5'-bis(pyri

  8. Asymmetric synthesis of aromatic β-amino acids using ω-transaminase: Optimizing the lipase concentration to obtain thermodynamically unstable β-keto acids.

    Science.gov (United States)

    Mathew, Sam; Jeong, Seong-Su; Chung, Taeowan; Lee, Sang-Hyeup; Yun, Hyungdon

    2016-01-01

    Synthesized aromatic β-amino acids have recently attracted considerable attention for their application as precursors in many pharmacologically relevant compounds. Previous studies on asymmetric synthesis of aromatic β-amino acids using ω-transaminases could not be done efficiently due to the instability of β-keto acids. In this study, a strategy to circumvent the instability problem of β-keto acids was utilized to generate β-amino acids efficiently via asymmetric synthesis. In this work, thermodynamically stable β-ketoesters were initially converted to β-keto acids using lipase, and the β-keto acids were subsequently aminated using ω-transaminase. By optimizing the lipase concentration, we successfully overcame the instability problem of β-keto acids and enhanced the production of β-amino acids. This strategy can be used as a general approach to efficiently generate β-amino acids from β-ketoesters.

  9. Asymmetric Synthesis of Natural Macrocyclic Diterpene(+)-Methyl Cembra-1,3,7,11-tetraene-16-carboxynate%(+)-Methyl Cembra-1,3,7,11-tetraene-16-carboxynate的不对称合成研究

    Institute of Scientific and Technical Information of China (English)

    孙彬; 梅天胜; 刘佐胜; 李裕林; 李瀛; 彭立增

    2005-01-01

    The first asymmetric synthesis of (+)-methyl cembra-1,3,7,11-tetraene-16-carboxynate, a naturally occurring cembrane-type macrocyclic diterpene isolated from Sinularia mayi, was achieved via general approach by employing an intramolecular McMurry coupling and Sharpless asymmetric epoxidation as the key steps from readily available starting materials. The synthesis presented here verifies that the absolute configuration of compound 1 was assumed as 15R.

  10. Catalytic Asymmetric Synthesis of Ketene Heterodimer β-Lactones: Scope and Limitations.

    Science.gov (United States)

    Chen, Shi; Ibrahim, Ahmad A; Peraino, Nicholas J; Nalla, Divya; Mondal, Mukulesh; Van Raaphorst, Maxwell; Kerrigan, Nessan J

    2016-09-01

    In this article we describe extensive studies of the catalytic asymmetric heterodimerization of ketenes to give ketene heterodimer β-lactones. The optimal catalytic system was determined to be a cinchona alkaloid derivative (TMS-quinine or Me-quinidine). The desired ketene heterodimer β-lactones were obtained in good to excellent yields (up to 90%), with excellent levels of enantioselectivity (≥90% ee for 33 Z and E isomer examples), good to excellent (Z)-olefin isomer selectivity (≥90:10 for 20 examples), and excellent regioselectivity (only one regioisomer formed). Full details of catalyst development studies, catalyst loading investigations, substrate scope exploration, protocol innovations (including double in situ ketene generation for 7 examples), and an application to a cinnabaramide A intermediate are described. The addition of lithium perchlorate (1-2 equiv) as an additive to the alkaloid catalyst system was found to favor formation of the E isomer of the ketene heterodimer. Ten examples were formed with moderate to excellent (E)-olefin isomer selectivity (74:25 to 97:3) and with excellent enantioselectivity (84-98% ee). PMID:27490092

  11. Synthesis, Annealing and Performance of Pd-Au Asymmetric Composite Membranes for Hydrogen Purification

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Yi Hua [Worcester Polytechnic Institute; Chen, Chao-Huang [Worcester Polytechnic Institute; Catalano, Jacopo [Worcester Polytechnic Institute; Guazzone, Federico [Worcester Polytechnic Institute; Payzant, E Andrew [ORNL

    2013-01-01

    Composite asymmetric Pd-Au membranes, based on porous Inconel and Hastelloy tubular supports, were prepared by means of electroless deposition and galvanic displacement techniques and tested, before and after Au deposition, in pure H2 atmosphere. The final membranes, with Au average bulk composition up to 16.7 wt%, were 9 15 m thick and showed, for the entire duration of characterization, H2/He ideal selectivity in excess of 900. The annealing of the as-prepared membranes was conducted through the coating and diffusion mechanism in He and H2 atmospheres at 500 C. The annealing conditions were chosen after non-isothermal and isothermal HT-XRD studies on coupons synthetized with similar preparation methods. After the formation of the Pd-Au layer, the membranes showed steady flux and a stable Au gradient on the membrane top layer. Comparisons between permeance for Pd/Au and pure Pd membranes indicated that the membranes with an Au average bulk composition of 4.5 and 5.4 wt% had an enhancement, up to 20%, of the H2 permeability in the temperature range 250 450 C with respect to pure Pd membranes. On the other hand, the membrane having the highest Au composition, 16.7 wt%, even though characterized by a lower H2 permeability (77% of pure Pd) had a rather high surface Au composition (approximately 46 wt%), which might provide good H2S poisoning tolerance.

  12. The Total Synthesis Problem of linear multivariable control. II - Unity feedback and the design morphism

    Science.gov (United States)

    Sain, M. K.; Antsaklis, P. J.; Gejji, R. R.; Wyman, B. F.; Peczkowski, J. L.

    1981-01-01

    Zames (1981) has observed that there is, in general, no 'separation principle' to guarantee optimality of a division between control law design and filtering of plant uncertainty. Peczkowski and Sain (1978) have solved a model matching problem using transfer functions. Taking into consideration this investigation, Peczkowski et al. (1979) proposed the Total Synthesis Problem (TSP), wherein both the command/output-response and command/control-response are to be synthesized, subject to the plant constraint. The TSP concept can be subdivided into a Nominal Design Problem (NDP), which is not dependent upon specific controller structures, and a Feedback Synthesis Problem (FSP), which is. Gejji (1980) found that NDP was characterized in terms of the plant structural matrices and a single, 'good' transfer function matrix. Sain et al. (1981) have extended this NDP work. The present investigation is concerned with a study of FSP for the unity feedback case. NDP, together with feedback synthesis, is understood as a Total Synthesis Problem.

  13. An Environmentally Benign System for Synthesis of β-Hydroxylketones: L-Histidine Asymmetrically Catalyzed Direct Aldol Reactions in Aqueous Micelle and Water-like Media

    Institute of Scientific and Technical Information of China (English)

    PENG Yi-Yuan; PENG Shu-Jun; DING Qiu-Ping; WANG Qi; CHENG Jin-Pei

    2007-01-01

    The first histidine catalyzed direct aldol reactions of ketones with nitrobenzaldehydes in water and in poly(ethylene glycol) (PEG) were reported. It reveals that histidine is a good aldol catalyst for synthesis of β-hydroxylketones in water and in PEG, giving good to excellent yields of the respective products. Better enantioand regioselectivity were achieved using low molecular weight PEG as the media. The results show that histidine and PEG-200 or -300 may constitute a promising environmentally benign system for asymmetric synthesis of β-hydroxylketones.

  14. The absolute configuration of (+)-oxopropaline D by theoretical calculation of specific rotation and asymmetric synthesis.

    Science.gov (United States)

    Kuwada, Takeshi; Fukui, Miyako; Hata, Toshiyuki; Choshi, Tominari; Nobuhiro, Junko; Ono, Yukio; Hibino, Satoshi

    2003-01-01

    The specific optical rotations of (R)-oxopropaline D calculated by two ab initio MO methods were +52+/-31 degrees and +61+/-29 degrees, respectively, and (+)-oxopropaline D (3) was presumed to have an R-configuration. On the basis of this theoretical result, the reaction of 1-litio-beta-carboline with (R)-glyceraldehyde acetonide followed by oxidation with MnO(2) gave (R)-oxopropaline D acetonide (4a), which was consistent with the previously synthesized (+)-oxopropaline D acetonide (4) in all respects. From the results of theoretical calculations and the experimental synthesis, we determined that natural (+)-oxopropaline D (3) has an R-configuration.

  15. Synthesis of asymmetric supramolecular compounds using a Ni(0) catalysed homo-coupling approach

    OpenAIRE

    Cassidy, Lynda; Horn, Sabine; Cleary, Laura; Halpin, Yvonne; Browne, Wesley R.; Vos, Johannes G.

    2009-01-01

    The synthesis and characterisation of a series of dinuclear ruthenium and osmium polypyridyl metal complexes based on the bridging ligands [5-(5'-bipyridin-2',2 ''-yl)-3-(pyridin-2-yl)]-1,2,4-triazole (Hpytr-bipy), 2,2 ''-bis(pyridin-2 '' yl)-5,5 ''-bis(pyridin-3 ''-yl) (bipy-bipy) and 5,5'-bis(pyridin-2 ''-yl)-3,3'-bis(1,2,4-triazole) (Hpytr-Hpytr) are reported. The dinuclear complexes have been synthesised via a Ni(0) catalysed cross-coupling reaction from brominated precursors. With this a...

  16. Asymmetric synthesis of quaternary aryl amino acid derivatives via a three-component aryne coupling reaction

    Directory of Open Access Journals (Sweden)

    Elizabeth P. Jones

    2011-11-01

    Full Text Available A method was developed for the synthesis of α-alkyl, α-aryl-bislactim ethers in good to excellent yields and high diastereoselectivities, consisting of a facile one-pot procedure in which the aryl group is introduced by means of a nucleophilic addition to benzyne and the alkyl group by alkylation of a resultant benzylic anion. Hydrolysis of the sterically less hindered adducts gave the corresponding quaternary amino acids with no racemization, whereas hydrolytic ring opening gave the corresponding valine dipeptides from bulkier bislactims.

  17. Synthesis of chiral lactams via asymmetric hydrogenation of α,β-unsaturated nitriles.

    Science.gov (United States)

    Kong, Duanyang; Li, Meina; Zi, Guofu; Hou, Guohua

    2016-04-26

    A highly efficient Rh-catalyzed enantioselective hydrogenation of α,β-unsaturated nitriles containing ester/amide groups has been developed. Under mild conditions, with a complex of rhodium and (S,S)-f-spiroPhos as the catalyst, a variety of α,β-unsaturated nitriles bearing an ester or amide group were successfully hydrogenated to the corresponding chiral nitriles with excellent enantioselectivities (up to 99.7% ee) and high turnover numbers (TON = 10 000). Furthermore, this catalyst system was also successfully applied to the synthesis of important chiral pharmacophore fragments, lactams, Paroxetine and amino acids. PMID:27056402

  18. Total synthesis of microcin B17 via a fragment condensation approach.

    Science.gov (United States)

    Thompson, Robert E; Jolliffe, Katrina A; Payne, Richard J

    2011-02-18

    The total synthesis of the 43 amino acid antibacterial peptide Microcin B17 (MccB17) is described. The natural product was synthesized via a convergent approach from a heterocycle-derived peptide and peptide thioester fragments prepared via Fmoc-strategy solid phase peptide synthesis (SPPS). Final assembly was achieved in an efficient manner using two Ag(I)-assisted peptide ligation reactions to afford MccB17 in excellent overall yield.

  19. Total synthesis of furospongolide and related furanolipid analogues as potential anti-tumour agents

    OpenAIRE

    Harrold, Donal Patrick

    2014-01-01

    This thesis details the design, development and execution of innovative methodology in the total synthesis of the terpene-derived marine natural product, furospongolide. It also outlines the synthetic routes used to prepare a novel range of furanolipids derivatives and subsequent evaluation of their potential as antitumour agents. The first chapter is a review of the literature describing efforts undertaken towards the synthesis of biologically active furanosesterterpenoid marine natural prod...

  20. Total synthesis of (3S, 5R, 3'S, 5'R)-capsorubin

    Energy Technology Data Exchange (ETDEWEB)

    Frederico, Daniel; Constantino, Mauricio G.; Donate, Paulo M. [Universidade de Sao Paulo (USP), Ribeirao Preto, SP (Brazil). Faculdade de Filosofia, Ciencias e Letras. Dept. de Quimica

    2009-07-01

    The total synthesis of enantiomerically enriched (3S, 5R, 3'S, 5'R)-capsorubin (1) by aldol condensation of (1R, 4S)-1-(4-hydroxy-1,2,2-trimethyl-cyclopentyl)ethanone (2a) and crocetindial (3) is described. An alternative, short eight-step synthesis of the optically active compound 2a (ee 89%) is also reported. (author)

  1. Stereoselective total synthesis of the potent anti-asthmatic compound CMI-977 (LDP-977)

    Energy Technology Data Exchange (ETDEWEB)

    Dias, Luiz Carlos; Farina, Lui Strambi; Ferreira, Marco Antonio Barbosa, E-mail: ldias@iqm.unicamp.br [Universidade de Campinas (UNICAMP), SP (Brazil). Instituto de Quimica

    2013-02-15

    A short and efficient stereoselective total synthesis of CMI-977 (LDP-977), a potent and orally active anti-asthmatic compound, was developed. The key steps involve a highly diastereoselective Mukaiyama oxidative cyclization, which provides the trans-THF (tetrahydrofuran) unit and a Seyferth-Gilbert homologation to construct the triple bond in the target molecule. The synthesis of the key chiral building block was performed using Jacobsen hydrolytic kinetic resolution. (author)

  2. Total Synthesis of Ionic Liquid Systems for Dissolution of Lunar Simulant

    Science.gov (United States)

    Sharpe, Robert J.; Karr, Laurel J.; Paley, Mark S.

    2010-01-01

    For purposes of Space Resource Utilization, work in the total synthesis of a new ionic liquid system for the extraction of oxygen and metals from lunar soil is studied and described. Reactions were carried out according to procedures found in the chemical literature, analyzed via Thin-Layer Chromatography and 1H Nuclear Magnetic Resonance Spectroscopy and purified via vacuum distillation and rotary evaporation. Upon final analysis via 1H NMR, it was found that while the intermediates of the synthesis had been achieved, unexpected side products were also present. The mechanisms and constraints of the synthesis are described as well as the final results of the project and recommendations for continued study

  3. Development of a large scale asymmetric synthesis of the glucocorticoid agonist BI 653048 BS H3PO4.

    Science.gov (United States)

    Reeves, Jonathan T; Fandrick, Daniel R; Tan, Zhulin; Song, Jinhua J; Rodriguez, Sonia; Qu, Bo; Kim, Soojin; Niemeier, Oliver; Li, Zhibin; Byrne, Denis; Campbell, Scot; Chitroda, Ashish; DeCroos, Phil; Fachinger, Thomas; Fuchs, Victor; Gonnella, Nina C; Grinberg, Nelu; Haddad, Nizar; Jäger, Burkhard; Lee, Heewon; Lorenz, Jon C; Ma, Shengli; Narayanan, Bikshandarkoil A; Nummy, Larry J; Premasiri, Ajith; Roschangar, Frank; Sarvestani, Max; Shen, Sherry; Spinelli, Earl; Sun, Xiufeng; Varsolona, Richard J; Yee, Nathan; Brenner, Michael; Senanayake, Chris H

    2013-04-19

    The development of a large scale synthesis of the glucocorticoid agonist BI 653048 BS H3PO4 (1·H3PO4) is presented. A key trifluoromethyl ketone intermediate 22 containing an N-(4-methoxyphenyl)ethyl amide was prepared by an enolization/bromine-magnesium exchange/electrophile trapping reaction. A nonselective propargylation of trifluoromethyl ketone 22 gave the desired diastereomer in 32% yield and with dr = 98:2 from a 1:1 diastereomeric mixture after crystallization. Subsequently, an asymmetric propargylation was developed which provided the desired diastereomer in 4:1 diastereoselectivity and 75% yield with dr = 99:1 after crystallization. The azaindole moiety was efficiently installed by a one-pot cross coupling/indolization reaction. An efficient deprotection of the 4-methoxyphenethyl group was developed using H3PO4/anisole to produce the anisole solvate of the API in high yield and purity. The final form, a phosphoric acid cocrystal, was produced in high yield and purity and with consistent control of particle size. PMID:23544738

  4. Total Synthesis of (+)-Cytosporolide A via a Biomimetic Hetero-Diels-Alder Reaction.

    Science.gov (United States)

    Takao, Ken-Ichi; Noguchi, Shuji; Sakamoto, Shu; Kimura, Mizuki; Yoshida, Keisuke; Tadano, Kin-Ichi

    2015-12-23

    The first total synthesis of (+)-cytosporolide A was achieved by a biomimetic hetero-Diels-Alder reaction of (-)-fuscoatrol A with o-quinone methide generated from (+)-CJ-12,373. The dienophile, highly oxygenated caryophyllene sesquiterpenoid (-)-fuscoatrol A, was synthesized from the synthetic intermediate in our previous total synthesis of (+)-pestalotiopsin A. The o-quinone methide precursor, isochroman carboxylic acid (+)-CJ-12,373, was synthesized through a Kolbe-Schmitt reaction and an oxa-Pictet-Spengler reaction. The hetero-Diels-Alder reaction of these two compounds proceeded with complete chemo-, regio-, and stereoselectivity to produce the complicated pentacyclic ring system of the cytosporolide skeleton. This total synthesis unambiguously demonstrates that natural cytosporolide A has the structure previously suggested. PMID:26633257

  5. Streamlined Total Synthesis of Uncialamycin and Its Application to the Synthesis of Designed Analogues for Biological Investigations.

    Science.gov (United States)

    Nicolaou, K C; Wang, Yanping; Lu, Min; Mandal, Debashis; Pattanayak, Manas R; Yu, Ruocheng; Shah, Akshay A; Chen, Jason S; Zhang, Hongjun; Crawford, James J; Pasunoori, Laxman; Poudel, Yam B; Chowdari, Naidu S; Pan, Chin; Nazeer, Ayesha; Gangwar, Sanjeev; Vite, Gregory; Pitsinos, Emmanuel N

    2016-07-01

    From the enediyne class of antitumor antibiotics, uncialamycin is among the rarest and most potent, yet one of the structurally simpler, making it attractive for chemical synthesis and potential applications in biology and medicine. In this article we describe a streamlined and practical enantioselective total synthesis of uncialamycin that is amenable to the synthesis of novel analogues and renders the natural product readily available for biological and drug development studies. Starting from hydroxy- or methoxyisatin, the synthesis features a Noyori enantioselective reduction, a Yamaguchi acetylide-pyridinium coupling, a stereoselective acetylide-aldehyde cyclization, and a newly developed annulation reaction that allows efficient coupling of a cyanophthalide and a p-methoxy semiquinone aminal to forge the anthraquinone moiety of the molecule. Overall, the developed streamlined synthesis proceeds in 22 linear steps (14 chromatographic separations) and 11% overall yield. The developed synthetic strategies and technologies were applied to the synthesis of a series of designed uncialamycin analogues equipped with suitable functional groups for conjugation to antibodies and other delivery systems. Biological evaluation of a select number of these analogues led to the identification of compounds with low picomolar potencies against certain cancer cell lines. These compounds and others like them may serve as powerful payloads for the development of antibody drug conjugates (ADCs) intended for personalized targeted cancer therapy. PMID:27266267

  6. Process Considerations for the Asymmetric Synthesis of Chiral Amines using ω-Transaminase

    DEFF Research Database (Denmark)

    Lima Afonso Neto, Watson

    improve its stability and allow recycling and easy separation; (ii) the use of controlled release of substrate (fed-batch) or in situ substrate supply – (ISSS) to decrease substrate inhibition and deal with the substrate low solubility; and (iii) the use of in situ product (ISPR) and co-product removal...... (IScPR) to respectively alleviate product inhibition and shift the reaction equilibrium. From an academic point of view, more important than the implementation of these technologies to a specific example, is the development of a general methodology that can be later applied in other cases. Hence, this......) the selection of suitable polymeric resins for product removal. The work has been performed in collaboration with c-LEcta GmbH (Leipzig, Germany) and DSM Innovative Synthesis (Geleen, The Netherlands) who supplied the enzymes for the case study, making possible the successful demonstration of the...

  7. Heronapyrrole D: A case of co-inspiration of natural product biosynthesis, total synthesis and biodiscovery

    Directory of Open Access Journals (Sweden)

    Jens Schmidt

    2014-05-01

    Full Text Available The heronapyrroles A–C have first been isolated from a marine-derived Streptomyces sp. (CMB-0423 in 2010. Structurally, these natural products feature an unusual nitropyrrole system to which a partially oxidized farnesyl chain is attached. The varying degree of oxidation of the sesquiterpenyl subunit in heronapyrroles A–C provoked the hypothesis that there might exist other hitherto unidentified metabolites. On biosynthetic grounds a mono-tetrahydrofuran-diol named heronapyrrole D appeared a possible candidate. We here describe a short asymmetric synthesis of heronapyrrole D, its detection in cultivations of CMB-0423 and finally the evaluation of its antibacterial activity. We thus demonstrate that biosynthetic considerations and the joint effort of synthetic and natural product chemists can result in the identification of new members of a rare class of natural products.

  8. Enantioselective Total Synthesis of (+)-Steenkrotin A and Determination of Its Absolute Configuration.

    Science.gov (United States)

    Pan, Saiyong; Gao, Beiling; Hu, Jialei; Xuan, Jun; Xie, Hujun; Ding, Hanfeng

    2016-01-18

    The first enantioselective total synthesis of (+)-steenkrotin A has been achieved in 18 steps and 4.2 % overall yield. The key features of the strategy entail a Rh-catalyzed O-H bond insertion followed by an intramolecular carbonyl-ene reaction, two sequential SmI2 -mediated Ueno-Stork and ketyl-olefin cyclizations, and a cascade intramolecular aldol condensation/vinylogous retro-aldol/aldol process with inversion of the relative configuration at the C7 position. The absolute configuration of (+)-steenkrotin A was determined based on the stepwise construction of the stereocenters during the total synthesis. PMID:26660855

  9. Chiral Borated Esters in Asymmetric Synthesis:1.The First Asymmetric Reaction Catalyzed by Chiral Spiroborated Esters with an O3BN Framework

    Institute of Scientific and Technical Information of China (English)

    LIU, De-Jun(刘德军); SHAN, Zi-Xing(单自兴); QIN, Jin-Gui(秦金贵)

    2004-01-01

    The first asymmetric reaction catalyzed by chiral spiroborated esters with an O3BN framework was reported. In the presence of 0.1 equivalent of (R,S)-1 or (S,S)-1, acetophenone was reduced by 0.6 equivalent of borane in THF at 0-5 ℃ for 2 h to give (R)-1-phenylethanol of up to 76% ee and 73% isolated yield. Influence of reaction conditions on the stereoselectivity of the reduction was investigated and a possible catalytic mechanism of the chiral spiroborated esters toward the reduction was also suggested.

  10. Asymmetric chemoenzymatic synthesis of miconazole and econazole enantiomers. The importance of chirality in their biological evaluation.

    Science.gov (United States)

    Mangas-Sánchez, Juan; Busto, Eduardo; Gotor-Fernández, Vicente; Malpartida, Francisco; Gotor, Vicente

    2011-04-01

    A simple and novel chemoenzymatic route has been applied for the first time in the synthesis of miconazole and econazole single enantiomers. Lipases and oxidoreductases have been tested in stereoselective processes; the best results were attained with oxidoreductases for the introduction of chirality in an adequate intermediate. The behaviors of a series of ketones and racemic alcohols in bioreductions and acetylation procedures, respectively, have been investigated; the best results were found with alcohol dehydrogenases A and T, which allowed the production of (R)-2-chloro-1-(2,4-dichlorophenyl)ethanol in enantiopure form under very mild reaction conditions. Final chemical modifications have been performed in order to isolate the target fungicides miconazole and econazole both as racemates and as single enantiomers. Biological evaluation of the racemates and single enantiomers has shown remarkable differences against the growth of several microorganisms; while (R)-miconazole seemed to account for most of the biological activity of racemic miconazole on all the strains tested, both enantiomers of econazole showed considerable biological activities. In this manner, (R)-econazole showed higher values against Candida krusei , while higher values were observed for (S)-econazole against Cryptococcus neoformans, Penicillium chrysogenum, and Aspergillus niger. PMID:21384803

  11. De novo asymmetric synthesis and biological analysis of the daumone pheromones in Caenorhabditis elegans and in the soybean cyst nematode Heterodera glycines

    Science.gov (United States)

    The de novo asymmetric total syntheses of daumone 1, daumone 2 and analogs are described. The key steps of our approach are the diastereoselective palladium catalyzed glycosylation reaction, the Noyori reduction of a acetylfuran and a propargyl ketone, which introduce the absolute stereochemistry of...

  12. Chemistry of Renieramycins. Part 14: Total Synthesis of Renieramycin I and Practical Synthesis of Cribrostatin 4 (Renieramycin H

    Directory of Open Access Journals (Sweden)

    Masashi Yokoya

    2015-08-01

    Full Text Available The first total synthesis of (±-renieramycin I, which was isolated from the Indian bright blue sponge Haliclona cribricutis, is described. The key step is the selenium oxide oxidation of pentacyclic bis-p-quinone derivative (3 stereo- and regioselectively. We also report a large-scale synthesis of cribrostatin 4 (renieramycin H via the C3-C4 double bond formation in an early stage based on the Avendaño’s protocol, from readily available 1-acetyl-3-(3-methyl-2,4,5-trimethylphenylmethyl-piperazine-2,5-dione (8 in 18 steps (8.3% overall yield. The synthesis provides unambiguous evidence supporting the original structure of renieramycin I.

  13. Formal Total Synthesis of Diazonamide A by Indole Oxidative Rearrangement.

    Science.gov (United States)

    David, Nadège; Pasceri, Raffaele; Kitson, Russell R A; Pradal, Alexandre; Moody, Christopher J

    2016-07-25

    A short formal total synthesis of the marine natural product diazonamide A is described. The route is based on indole oxidative rearrangement, and a number of options were investigated involving migration of tyrosine or oxazole fragments upon oxidation of open chain or macrocyclic precursors. The final route proceeds from 7-bromoindole by sequential palladium-catalysed couplings of an oxazole fragment at C-2, followed by a tyrosine fragment at C-3. With the key 2,3-disubstituted indole readily in hand, formation of a macrocyclic lactam set the stage for the crucial oxidative rearrangement to a 3,3-disubstituted oxindole. Notwithstanding the concomitant formation of the unwanted indoxyl isomer, the synthesis successfully delivered, after deprotection, the key oxindole intermediate, thereby completing a formal total synthesis of diazonamide A. PMID:27346186

  14. Asymmetric Synthesis of Spirocyclic 2-Benzopyrans for Positron Emission Tomography of σ1 Receptors in the Brain

    Directory of Open Access Journals (Sweden)

    Katharina Holl

    2014-01-01

    Full Text Available Sharpless asymmetric dihydroxylation of styrene derivative 6 afforded chiral triols (R-7 and (S-7, which were cyclized with tosyl chloride in the presence of Bu2SnO to provide 2-benzopyrans (R-4 and (S-4 with high regioselectivity. The additional hydroxy moiety in the 4-position was exploited for the introduction of various substituents. Williamson ether synthesis and replacement of the Boc protective group with a benzyl moiety led to potent σ1 ligands with high σ1/σ2-selectivity. With exception of the ethoxy derivative 16, the (R-configured enantiomers represent eutomers with eudismic ratios of up to 29 for the ester (R-18. The methyl ether (R-15 represents the most potent σ1 ligand of this series of compounds, with a Ki value of 1.2 nM and an eudismic ratio of 7. Tosylate (R-21 was used as precursor for the radiosynthesis of [18F]-(R-20, which was available by nucleophilic substitution with K[18F]F K222 carbonate complex. The radiochemical yield of [18F]-(R-20 was 18%–20%, the radiochemical purity greater than 97% and the specific radioactivity 175–300 GBq/µmol. Although radiometabolites were detected in plasma, urine and liver samples, radiometabolites were not found in brain samples. After 30 min, the uptake of the radiotracer in the brain was 3.4% of injected dose per gram of tissue and could be reduced by coadministration of the σ1 antagonist haloperidol. [18F]-(R-20 was able to label those regions of the brain, which were reported to have high density of σ1 receptors.

  15. Catalytic Macrocyclization Strategies Using Continuous Flow: Formal Total Synthesis of Ivorenolide A.

    Science.gov (United States)

    de Léséleuc, Mylène; Godin, Éric; Parisien-Collette, Shawn; Lévesque, Alexandre; Collins, Shawn K

    2016-08-01

    A formal total synthesis of ivorenolide A has been accomplished employing a Z-selective olefin cross metathesis and a macrocyclic Glaser-Hay coupling as key steps. The macrocyclization protocol employed a phase separation/continuous flow manifold whose advantages include catalysis, fast reaction times, high concentrations, and facile scale-up. PMID:27404899

  16. The first total synthesis of the novel triquinane natural products pleurotellol and pleurotellic acid

    OpenAIRE

    Mehta, Goverdhan; Murthy, Sai Krishna A

    2003-01-01

    The first total synthesis of the triquinane based sesquiterpenoid antibiotics (±)-pleurotellol and (±)-pleurotellic acid isolated from the fermentation broth of Pleurotellus hypnophilus have been accomplished. The triquinane based bis-enone system obtained via photo-thermal metathesis in a caged pentacyclic dione has been elaborated to the natural products through carefully crafted functional group transformations.

  17. First total synthesis of yanuthones: novel farnesylated epoxycyclohexenoid marine natural products

    OpenAIRE

    Mehta, Goverdhan; Pan, Subhas Chandra

    2005-01-01

    The total synthesis of the recently isolated marine natural products of mixed biosynthetic origin, yanuthones A, 13 C and 22-deacylyanuthone A,has been accomplished following a short regio- and stereocontrolled approach involving the key intermediacy of 2-farnesyl-p-benzoquinone.

  18. Selective bromochlorination of a homoallylic alcohol for the total synthesis of (−)-anverene

    Science.gov (United States)

    Seidl, Frederick J

    2016-01-01

    Summary The scope of a recently reported method for the catalytic enantioselective bromochlorination of allylic alcohols is expanded to include a specific homoallylic alcohol. Critical factors for optimization of this reaction are highlighted. The utility of the product bromochloride is demonstrated by the first total synthesis of an antibacterial polyhalogenated monoterpene, (−)-anverene. PMID:27559385

  19. First Total Synthesis of an Analogue of (±)—Hypargenin B

    Institute of Scientific and Technical Information of China (English)

    AnPaiLI; HuiWANG; 等

    2002-01-01

    First total synthesis of (±)-hypargenin B methyl ether 2 was accomplished via a strategy of AC→ABC,in which CrO3/H2O/NaOAc/HOAc system was utilized for introducing 7-keto group in order to aviod dehydration of benzyl tertiary alcohol.

  20. Total Synthesis and Complete Stereostructure of a Marine Macrolide Glycoside, (-)-Lyngbyaloside B.

    Science.gov (United States)

    Fuwa, Haruhiko; Yamagata, Naoya; Okuaki, Yuta; Ogata, Yuya; Saito, Asami; Sasaki, Makoto

    2016-05-10

    We have described in detail the total synthesis of both the proposed and correct structures of (-)-lyngbyaloside B, which facilitated the elucidation of the complete stereostructure of this natural product. Our study began with the total synthesis of 13-demethyllyngbyaloside B, in which an esterification/ring-closing metathesis (RCM) strategy was successfully used for the efficient construction of the macrocycle. We also established reliable methods for the introduction of the conjugated diene side chain and the l-rhamnose residue onto the macrocyclic framework. However, the esterification/RCM strategy proved ineffective for the parent natural product because of the difficulties in acylating the sterically encumbered C-13 tertiary alcohol; macrolactionization of a seco-acid was also extensively investigated under various conditions without success. We finally completed the total synthesis of the proposed structure of (-)-lyngbyaloside B by means of a macrolactonization that involves an acyl ketene as the reactive species. However, the NMR spectroscopic data of our synthetic material did not match those of the authentic material, which indicated that the proposed structure must be re-examined. Inspection of the NMR spectroscopic data of the natural product and molecular mechanics calculations led us to postulate that the configuration of the C-10, C-11, and C-13 stereogenic centers had been incorrectly assigned in the proposed structure. Finally, our revised structure of (-)-lyngbyaloside B was unambiguously verified through total synthesis. PMID:27112323

  1. Buchner and Beyond: Arene Cyclopropanation as Applied to Natural Product Total Synthesis

    OpenAIRE

    Reisman, Sarah E.; Nani, Roger R.; Levin, Sergiy

    2011-01-01

    Buchner and Curtius first reported the cyclopropanation of arenes in 1885. Since the initial discovery, the Buchner reaction has been the subject of significant research by both physical and synthetic organic chemists. Described herein is a brief overview of the Buchner reaction and related arene cyclopropanation processes, with an emphasis on their application to natural product total synthesis.

  2. First Total Synthesis of an Analogue of (±)-Hypargenin B

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    First total synthesis of (±)-hypargenin B methyl ether 2 was accomplished via a  strategy of AC→ABC, in which CrO3/H2O/NaOAc/HOAc system was utilized for introducing  7-keto group in order to avoid dehydration of benzyl tertiary alcohol.

  3. First Total Synthesis of (±)-Abieta-8, 11, 13-trien-7β-ol

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The first total synthesis of (±)-abieta-8, 11, 13-trien-7β-ol (7) was accomplished via a strategy of AC→ABC, in which the reduction of the ketone 6 with LiAlH4 gave exclusively the title compound.

  4. Total synthesis of exiguamines A and B inspired by catecholamine chemistry.

    Science.gov (United States)

    Sofiyev, Vladimir; Lumb, Jean-Philip; Volgraf, Matthew; Trauner, Dirk

    2012-04-16

    The evolution of a total synthesis of the exiguamines, two structurally unusual natural products that are highly active inhibitors of indolamine-2,3-dioxygenase (IDO), is described. The ultimately successful strategy involves advanced cross-coupling methodology and features a potentially biosynthetic tautomerization/electrocyclization cascade reaction that forms two heterocycles and installs a quaternary ammonium ion in a single synthetic operation.

  5. Cu-Mediated Stille Reactions of Sterically Congested Fragments: Towards the Total Synthesis of Zoanthamine

    DEFF Research Database (Denmark)

    Nielsen, Thomas E.; Le Quement, Sebastian; Juhl, Martin;

    2005-01-01

    A study on the Stille reaction of alkenyl iodides and starmanes with structural resemblance to retrosynthetic fragments of a projected total synthesis of the marine alkaloid zoanthamine was carried out. A range of reaction conditions was examined, and a protocol developed by Corey utilizing exces...

  6. Position dependence of the particle density in a double-chain section of a linear network in a totally asymmetric simple exclusion process

    Science.gov (United States)

    Pesheva, N. C.; Brankov, J. G.

    2013-06-01

    We report here results on the study of the totally asymmetric simple exclusion process, defined on an open network, consisting of head and tail simple-chain segments with a double-chain section inserted in between. Results of numerical simulations for relatively short chains reveal an interesting feature of the network. When the current through the system takes its maximum value, a simple translation of the double-chain section forward or backward along the network leads to a sharp change in the shape of the density profiles in the parallel chains, thus affecting the total number of particles in that part of the network. In the symmetric case of equal injection and ejection rates α=β>1/2 and equal lengths of the head and tail sections, the density profiles in the two parallel chains are almost linear, characteristic of the coexistence line (shock phase). Upon moving the section forward (backward), their shape changes to the one typical for the high- (low-) density phases of a simple chain. The total bulk density of particles in a section with a large number of parallel chains is evaluated too. The observed effect might have interesting implications for the traffic flow control as well as for biological transport processes in living cells. An explanation of this phenomenon is offered in terms of a finite-size dependence of the effective injection and ejection rates at the ends of the double-chain section.

  7. Contemporary Strategies for the Synthesis of Tetrahydropyran Derivatives: Application to Total Synthesis of Neopeltolide, a Marine Macrolide Natural Product

    Science.gov (United States)

    Fuwa, Haruhiko

    2016-01-01

    Tetrahydropyrans are structural motifs that are abundantly present in a range of biologically important marine natural products. As such, significant efforts have been paid to the development of efficient and versatile methods for the synthesis of tetrahydropyran derivatives. Neopeltolide, a potent antiproliferative marine natural product, has been an attractive target compound for synthetic chemists because of its complex structure comprised of a 14-membered macrolactone embedded with a tetrahydropyran ring, and twenty total and formal syntheses of this natural product have been reported so far. This review summarizes the total and formal syntheses of neopeltolide and its analogues, highlighting the synthetic strategies exploited for constructing the tetrahydropyran ring. PMID:27023567

  8. The Total Synthesis of Insect Antifeedant (-)-Dihydroclerodin Starting from R-(-)-Carvone

    OpenAIRE

    Meulemans, T.M.

    2000-01-01

    The first total synthesis of the natural enantiomer of the insect-antifeedant dihydroclerodin ( 1 ) and lupulin C ( 268 ) has been achieved in 18 and 17 steps respectively starting from R-(-)-carvone ( 2 ). A new strategy was developed in which the hexahydrofuro[2,3- b ]furan fragment was introduced in the beginning of the synthesis, via a remarkably diastereoselective Mukaiyama reaction of silyl enol ether 135 with 2-methoxy-hexahydrofuro[2,3- b ]furan ( 156 ), which gave only two of the pos...

  9. L-Tartaric Acid as a New Chiral Auxiliary for Asymmetric Synthesis of Piperazinones, Morpholinones, Dihydroquinoxalinones and Dihydrobenzoxazinones

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Yelim; Park, Kon Ji; Park, Yong Sun [Konkuk Univ., Seoul (Korea, Republic of)

    2012-11-15

    We have reported the dynamic resolution of α-bromo esters in nucleophilic substitution using L-tartaric acid derivatives as a new effective chiral auxiliary. In the substitutions with ethylenediamine and 2-aminoethanol nucleophiles, spontaneous cyclization can provide a convenient procedure for asymmetric syntheses of 3-substituted piperazin-2-ones and morpholin-2-ones. In addition, the substitutions with arylamine nucleophiles such as 1,2-diaminobenzene and 2-aminophenol can provide an efficient method for asymmetric syntheses of dihydroquinoxalinones and dihydrobenzoxazinones. The simple protocol with mild condition suggests further applications to asymmetric syntheses of various heterocyclic compounds.

  10. The background of the total synthesis of yeast alanine transfer RNA

    Institute of Scientific and Technical Information of China (English)

    QI GuoRong

    2010-01-01

    @@ The research findings concerning the total synthesis of yeast alanine transfer RNA (yeast alanine tRNA) were successively published in Chinese Science Bulletin (1982) and Science in China (1983) [1].The research work started in 1968 and was finished in November 1981.It was the first artificial synthesis of a nucleic acid molecule, which followed the first artificial synthesis of protein, crystalline bovine insulin, in China in 1965, both scientific milestones occurring in China.The composition, sequence and biological functions of the synthesized nucleic acid were identical to those of the natural yeast alanine tRNA.The research lasted for 13 years.From 1982 to 1984, one of the investigators in charge of the research Prof.

  11. Enantioselective synthesis of aziridines using asymmetric transfer hydrogenation as a precursor for chiral derivatives used as bonding agent for rocket solid propellants

    Directory of Open Access Journals (Sweden)

    Aparecida M. Kawamoto

    2002-11-01

    Full Text Available A rapid, expedient and enantioselective method for the synthesis of beta-hydroxy amines and monosubstituted aziridines in up to 99% e.e., via asymmetric transfer hydrogenation of a-amino ketones and cyclisation through treatment with tosyl chloride and base, is described. (1R,2R-N-(para-toluenesulfonyl-1,2-ethylenediamine with formic acid has been utilised as a ligand for the Ruthenium (II catalysed enantioselective transfer hydrogenation of the ketones.The chiral 2-methyl aziridine, which is a potentially more efficient bonding agent for Rocket Solid Propellant has been successfully achieved.

  12. Poly (ethylene oxide)-block-poly (n-butyl acrylate)-blockpoly (acrylic acid) triblock terpolymers with highly asymmetric hydrophilic blocks: synthesis and aqueous solution properties

    OpenAIRE

    Petrov, P; Yoncheva, K. (Krassimira); Mokreva, P. (Pavlina); Konstantinov, S.; J M Irache; Müller, A.H.E. (Axel H.E.)

    2013-01-01

    The synthesis and aggregation behaviour in aqueous media of novel amphiphilic poly(ethylene oxide)- block-poly(n-butyl acrylate)-block-poly(acrylic acid) (PEO–PnBA–PAA) triblock terpolymers were studied. Terpolymers composed of two highly asymmetric hydrophilic PEO (113 monomer units) and PAA (10–17 units) blocks, and a longer soft hydrophobic PnBA block (163 or 223 units) were synthesized by atom transfer radical polymerisation (ATRP) of n-butyl acrylate and tert-butyl acrylate ...

  13. The concise synthesis of chiral tfb ligands and their application to the rhodium-catalyzed asymmetric arylation of aldehydes

    OpenAIRE

    Nishimura, Takahiro; Kumamoto, Hana; Nagaosa, Makoto; Hayashi, Tamio

    2009-01-01

    New C2-symmetric tetrafluorobenzobarrelene ligands were prepared and applied successfully to the rhodium-catalyzed asymmetric addition of arylboronic acids to aromatic aldehydes giving chiral diarylmethanols in high yield with high enantioselectivity.

  14. Asymmetric synthesis of gem-diaryl substituted cyclic sulfamidates and sulfamides by rhodium-catalyzed arylation of cyclic ketimines.

    Science.gov (United States)

    Nishimura, Takahiro; Ebe, Yusuke; Fujimoto, Hiroto; Hayashi, Tamio

    2013-06-18

    Asymmetric addition of arylboronates to aryl-substituted cyclic ketimines proceeded in the presence of a rhodium catalyst coordinated with a chiral diene ligand to give high yields of sulfamidates and sulfamides with high enantioselectivity (up to 99% ee).

  15. Improved synthesis of cyclic tertiary allylic alcohols by asymmetric 1,2-addition of AlMe3 to enones.

    Science.gov (United States)

    Kolb, Andreas; Zuo, Wei; Siewert, Jürgen; Harms, Klaus; von Zezschwitz, Paultheo

    2013-11-25

    The development of an improved protocol for the enantioselective Rh(I) /binap-catalysed 1,2-addition of AlMe3 to cyclic enones is reported. (31)P NMR analysis of the reaction revealed that the catalyst in its resting state is a chloride-bridged dimer. This insight led to the use of AgBF4 as an additive for in situ activation of the dimeric precatalyst. Thus, the catalyst loading can now be reduced to only 1 mol% with respect to rhodium. Various 5-7-membered cyclic enones can be transformed into tertiary allylic alcohols with excellent levels of enantioselectivity and high yields. The obtained products are versatile synthetic building blocks, shown by a highly enantioselective formal total synthesis of the pheromone (-)-frontalin as well as formation of a bicyclic lactone that has the core structure of the natural flavour component "wine lactone".

  16. Studies towards the total synthesis of eleutherobin and other marine natural products

    OpenAIRE

    Mowat, Jeffrey Stuart

    2012-01-01

    The primary focus of the research described in this document relates to the development and application of new synthetic methodologies relevant for the concise construction of four natural products. In Chapter 2, a discussion of our investigation of the total synthesis of eleutherobin (1) is disclosed. Eleutherobin (1), first isolated in 1997 from the rare soft coral Eleutherobia sp., is a member of a class of microtubule stabilising natural products. Although it displays potent cytotoxicity,...

  17. Recent Advances in the Total Synthesis of Tetramic Acid-Containing Natural Products

    OpenAIRE

    Wen-Ju Bai; Chen Lu; Xiqing Wang

    2016-01-01

    With incredible bioactivities and fascinating structural complexities, tetramic acid- (TA-) containing natural products have attracted favorable attention among the organic chemistry community. Although the construction of the TA core is usually straightforward, the intricate C3-side chain sometimes asks for some deliberative strategy so as to fulfill an elegant total synthesis. This review mainly covers some exceptional synthetic examples for each type of natural product in recent years, sho...

  18. Total synthesis of the endogenous inflammation resolving lipid resolvin D2 using a common lynchpin

    OpenAIRE

    John Li; May May Leong; Alastair Stewart; Mark A. Rizzacasa

    2013-01-01

    The total synthesis of the endogenous inflammation resolving eicosanoid resolvin D2 (1) is described. The key steps involved a Wittig reaction between aldehyde 5 and the ylide derived from phosphonium salt 6 to give enyne 17 and condensation of the same ylide with aldehyde 7 to afford enyne 11. Desilylation of 11 followed by hydrozirconation and iodination gave the vinyl iodide 4 and Sonogashira coupling between this compound and enyne 3 provided alkyne 18. Acetonide deprotection, partial red...

  19. Total synthesis of (+)-discodermolide: a highly convergent fourth-generation approach.

    Science.gov (United States)

    Smith, Amos B; Freeze, B Scott; Xian, Ming; Hirose, Tomoyasu

    2005-04-28

    [structure: see text] A highly convergent, fourth-generation total synthesis of (+)-discodermolide (1), with a longest linear sequence of 17 steps and an overall yield of 9.0%, has been achieved. Highlighting the strategy is the efficient construction and sequential, bidirectional union of a linchpin comprising the C(9)-C(14) Wittig salt-vinyl iodide (-)-18. Importantly, Wittig salt generation proceeded in excellent yield under ambient pressure.

  20. Design, total synthesis, and evaluation of C13-C14 cyclopropane analogues of (+)-discodermolide.

    Science.gov (United States)

    Smith, Amos B; Xian, Ming; Liu, Fenghua

    2005-10-13

    [structure: see text] The design, total synthesis, and biological evaluation of two C13-C14-cyclopropyl analogues [(+)-1 and (+)-2] of (+)-discodermolide have been achieved. Key features of the syntheses include highly stereoselective, hydroxyl-directed cyclopropanations of vinyl iodides and higher order cuprate-mediated cross-coupling reactions between cyclopropyl iodides and alkyl iodides. Biological evaluation revealed that neither orientation of the cyclopropyl methylene completely substitutes for the C14 methyl found in (+)-discodermolide (3).

  1. First total synthesis of the marine natural products clavulolactones II and III.

    Science.gov (United States)

    Miller, Charlotte M; Benneche, Tore; Tius, Marcus A

    2015-04-01

    The first total synthesis of the marine prostanoids clavulolactones II and III is presented from an easily accessible chiral, non-racemic cyclopentenone intermediate. Key steps involve selective TBDMS deprotection, selective reduction of the β-side chain and aldol condensation. Clavulolactones II and III were successfully prepared from (S)-4-((tert-butyldimethylsilyl)oxy) cyclopent-2-en-1-one over nine steps, in overall yields of 21 and 7% respectively. PMID:25733336

  2. Total Synthesis of (±)-Paroxetine by Diastereoconvergent Cobalt-Catalysed Arylation

    OpenAIRE

    Despiau, Carole F; Dominey, Andrew P; Harrowven, David C.; Linclau, Bruno

    2014-01-01

    A total synthesis of paroxetine is reported, with a diastereoselective and diastereoconvergent cobalt-catalysed sp3–sp2 coupling reaction involving a 3-substituted 4-bromo-N-Boc-piperidine (Boc = tert-butoxycarbonyl) substrate as a key step. A 9:1 diastereoselectivity was obtained, while a control experiment involving a conformationally locked 3-substituted 4-bromo-tert-butyl cyclohexane ring proceeded with essentially complete stereoselectivity.

  3. A strategy for complex dimer formation when biomimicry fails: total synthesis of ten coccinellid alkaloids.

    Science.gov (United States)

    Sherwood, Trevor C; Trotta, Adam H; Snyder, Scott A

    2014-07-01

    Although dimeric natural products can often be synthesized in the laboratory by directly merging advanced monomers, these approaches sometimes fail, leading instead to non-natural architectures via incorrect unions. Such a situation arose during our studies of the coccinellid alkaloids, when attempts to directly dimerize Nature's presumed monomeric precursors in a putative biomimetic sequence afforded only a non-natural analogue through improper regiocontrol. Herein, we outline a unique strategy for dimer formation that obviates these difficulties, one which rapidly constructs the coccinellid dimers psylloborine A and isopsylloborine A through a terminating sequence of two reaction cascades that generate five bonds, five rings, and four stereocenters. In addition, a common synthetic intermediate is identified which allows for the rapid, asymmetric formal or complete total syntheses of eight monomeric members of the class. PMID:24959981

  4. LED 隧道灯透镜的全偏光设计%Totally Asymmetric Design of LED Lens for Tunnel Light

    Institute of Scientific and Technical Information of China (English)

    李柏林; 关烨锋; 罗婉霞

    2014-01-01

    A totally asymmetric design method for LED tunnel light lens is proposed , which is based on the mesh grids division of the LED light source with the theory of nonimaging optics .This method can not only have high energy utilization efficiency as the traditional lens , but also effectively reduce the glare effect for drivers while keeping in high uniformity of road surface luminance .A lighting simulation is made for the light distributions curve of the lens with DIALux , and it shows an excellent result with UE =0.88, UO =0.86, UI =0.91, TI=6.%运用非成像光学理论,基于LED能量网格划分的方法设计了一种全偏光的LED隧道灯透镜。该设计方法不仅具有传统偏光透镜中能量利用率高的优点,并且在保持高亮度均匀度的前提下,能有效地降低道路照明中眩目的影响。在照明分析软件DIALux中验证了该透镜,其配光曲线实现了UE =0.88, UO =0.86, UL =0.91, TI=6的良好照明效果。

  5. Metal-catalyzed Asymmetric Hetero-Diels-Alder Reactions of Unactivated Dienes with Glyoxylates

    DEFF Research Database (Denmark)

    Johannsen, Mogens; Yao, Sulan; Graven, Anette

    1998-01-01

    The development of a catalytic asymmetric hetero-Diels-Alder methodology for the reaction of unactivated dienes with glyoxylates is presented. Several different asymmetric catalysts can be used, but copper-bisoxazolines and aluminium-BINOL give the highest yield, and the best chemo- and...... enantioselectivities. The reaction course is dependent on several factors such as the solvent and the anions coordinated to the catalyst. The scope of the reaction is outlined by the total synthesis of a natural occurring actinidiolide....

  6. Natural Product Total Synthesis in the Organic Laboratory: Total Synthesis of Caffeic Acid Phenethyl Ester (CAPE), a Potent 5-Lipoxygenase Inhibitor from Honeybee Hives

    Science.gov (United States)

    Touaibia, Mohamed; Guay, Michel

    2011-01-01

    Natural products play a critical role in modern organic synthesis and learning synthetic techniques is an important component of the organic laboratory experience. In addition to traditional one-step organic synthesis laboratories, a multistep natural product synthesis is an interesting experiment to challenge students. The proposed three-step…

  7. Total Synthesis, Structure Revision, and Absolute Configuration of (−)-Brevenal

    Science.gov (United States)

    Fuwa, Haruhiko; Ebine, Makoto; Bourdelais, Andrea J.; Baden, Daniel G.; Sasaki, Makoto

    2008-01-01

    Total synthesis of structure 1 originally proposed for brevenal, a nontoxic polycyclic ether natural product isolated from the Florida red tide dinoflagellate, Karenia brevis, was accomplished. The key features of the synthesis involved (i) convergent assembly of the pentacyclic polyether skeleton based on our developed Suzuki–Miyaura coupling chemistry and (ii) stereoselective construction of the multi-substituted (E,E)-dienal side chain by using copper(I) thiophen-2-carboxylate (CuTC)-promoted modified Stille coupling. The disparity of NMR spectra between the synthetic material and the natural product required a revision of the proposed structure. Detailed spectroscopic comparison of synthetic 1 with natural brevenal, coupled with the postulated biosynthetic pathway for marine polyether natural products, suggested that the natural product was most likely represented by 2, the C26 epimer of the proposed structure 1. The revised structure was finally validated by completing the first total synthesis of (−)-2, which also unambiguously established the absolute configuration of the natural product. PMID:17177450

  8. Application of 3-Methyl-2-vinylindoles in Catalytic Asymmetric Povarov Reaction: Diastereo- and Enantioselective Synthesis of Indole-Derived Tetrahydroquinolines.

    Science.gov (United States)

    Dai, Wei; Jiang, Xiao-Li; Tao, Ji-Yu; Shi, Feng

    2016-01-01

    The first application of 3-methyl-2-vinylindoles in catalytic asymmetric Povarov reactions has been established via the three-component reactions of 3-methyl-2-vinylindoles, aldehydes, and anilines in the presence of chiral phosphoric acid, providing easy access to chiral indole-derived tetrahydroquinolines with three contiguous stereogenic centers at high yields (up to 99%) and with excellent diastereo- and enantioselectivities (all >95:5 dr, up to 96% ee). This mode of catalytic asymmetric three-component reaction offers a step-economic and atom-economic strategy for accessing enantioenriched indole-derived tetrahydroquinolines with structural diversity and complexity. PMID:26652222

  9. Towards a Catalytic Asymmetric Cope Rearrangement and the Synthesis and Self-Assembly of Metal-Coordinated Hosts

    OpenAIRE

    Moehlig, Melissa Padilla

    2013-01-01

    The Cope rearrangement has been used as the key step of several natural products but to date there is only one limited example in the literature that is capable of performing an asymmetric variant of this reaction. The first half of this dissertation focuses on our efforts towards performing a catalytic asymmetric Cope rearrangement to access remote stereocenters. The rearrangement of 2-formyl-1,5-dienes was achieved with both Brønsted and Lewis acid catalysts. The best Lewis acid catalyst wa...

  10. Non-cross-linked polystyrene-supported 2-imidazolidinone chiral auxiliary: synthesis and application in asymmetric alkylation reactions

    Science.gov (United States)

    Nguyen, Quynh Pham Bao

    2013-01-01

    Summary Asymmetric alkylation reactions using non-cross-linked polystyrene (NCPS)-supported 2-imidazolidinone chiral auxiliaries were successfully investigated with excellent diastereocontrol (>99% de). The recovery and the recycling of this soluble polymer-supported chiral auxiliary were achieved in order to produce highly optical pure carboxylic acids. PMID:24204423

  11. Synthesis of Novel Derivatives of (R)-Cysteine and Their Application in Asymmetric Reduction of Prochiral Ketones

    Institute of Scientific and Technical Information of China (English)

    WANG Hui; PEI Wei-wei; YE Wei-ping

    2005-01-01

    Novel chiral β-amino alcohols containing sulfide or sulfonyl groups were synthesized from (R)-cysteine. Their chiral induction in the asymmetric borane reduction of prochiral ketones was investigated. Optically active secondary alcohols with moderate or high e.e. values were obtained, and the causes of different enantioselectivities between these two sulfur-containing chiral β-amino alcohols were researched.

  12. Chiral dirhodium(II) carboxylates and carboxamidates as effective chemzymes in asymmetric synthesis of three-membered carbocycles.

    Science.gov (United States)

    Adly, Frady G; Ghanem, Ashraf

    2014-11-01

    In this review the recent advances in the utilization of two of the most important classes of dirhodium(II) paddlewheel complexes, dirhodium(II) carboxylates and carboxamidates, as chemzymes in inter- and intramolecular asymmetric cyclopropanation, as well as cyclopropenation reactions are discussed.

  13. Toward the Enantioselective Total Synthesis of Lyngbyatoxin A: On the Stereocontrolled Introduction of the Quaternary Stereogenic Centre

    DEFF Research Database (Denmark)

    Tønder, Janne Ejrnæs; Tanner, David Ackland

    2003-01-01

    This paper deals with an approach to the enantioselective total synthesis of Lyngbyatoxin A, with focus on the stereocontrolled introduction of the quaternary stereogenic centre. The key step in the synthesis involves an enantiospecific Lewis-acid mediated rearrangement of chiral vinyl epoxides c...

  14. Recent Advances in the Total Synthesis of Tetramic Acid-Containing Natural Products

    Directory of Open Access Journals (Sweden)

    Wen-Ju Bai

    2016-01-01

    Full Text Available With incredible bioactivities and fascinating structural complexities, tetramic acid- (TA- containing natural products have attracted favorable attention among the organic chemistry community. Although the construction of the TA core is usually straightforward, the intricate C3-side chain sometimes asks for some deliberative strategy so as to fulfill an elegant total synthesis. This review mainly covers some exceptional synthetic examples for each type of natural product in recent years, showcasing the great achievements as well as unsettled obstacles in this area, in the hope of accelerating the synthetic and biological investigations for this unique type of natural product.

  15. Total synthesis of leopolic acid A, a natural 2,3-pyrrolidinedione with antimicrobial activity

    Science.gov (United States)

    Dhavan, Atul A; Kaduskar, Rahul D; Musso, Loana; Scaglioni, Leonardo; Martino, Piera Anna

    2016-01-01

    Summary The first total synthesis of leopolic acid A, a fungal metabolite with a rare 2,3-pyrrolidinedione nucleus linked to an ureido dipeptide, was designed and carried out. Crucial steps for the strategy include a Dieckmann cyclization to obtain the 2,3-pyrrolidinedione ring and a Wittig olefination to install the polymethylene chain. An oxazolidinone-containing leopolic acid A analogue was also synthesized. The antibacterial activity showed by both compounds suggests that they could be considered as promising candidates for future developments. PMID:27559415

  16. Total Synthesis of Fellutamide B and Deoxy-Fellutamides B, C, and D

    Directory of Open Access Journals (Sweden)

    Richard J. Payne

    2013-07-01

    Full Text Available The total syntheses of the marine-derived lipopeptide natural product fellutamide B and deoxy-fellutamides B, C, and D are reported. These compounds were accessed through a novel solid-phase synthetic strategy using Weinreb amide-derived resin. As part of the synthesis, a new enantioselective route to (3R-hydroxy lauric acid was developed utilizing a Brown allylation reaction followed by an oxidative cleavage-oxidation sequence as the key steps. The activity of these natural products, and natural product analogues was also assessed against Mycobacterium tuberculosis in vitro.

  17. An approach to seco-prezizaane sesquiterpenoids: enantioselective total synthesis of (+)-1S-minwanenone.

    Science.gov (United States)

    Mehta, Goverdhan; Shinde, Harish M

    2012-09-21

    A strategy of general applicability toward seco-prezizaane sesquiterpenes, from a chiral, tricyclic synthon, readily available via an enzymatic resolution step from the Diels-Alder adduct of cyclopentadiene and p-benzoquinone, has been devised. Our approach enables harnessing of the stereochemical proclivities of the norbornyl system to install the desired stereochemistry at the key stereogenic centers. Recourse to an interesting stratagem to realign a stereochemical divergence into stereoreconvergence forms the cornerstone of our successful approach. The first total synthesis of (+)-1S-minwanenone, a prototypical member of seco-prezizaane subclass, has been accomplished. PMID:22897237

  18. Total synthesis of the endogenous inflammation resolving lipid resolvin D2 using a common lynchpin

    Directory of Open Access Journals (Sweden)

    John Li

    2013-12-01

    Full Text Available The total synthesis of the endogenous inflammation resolving eicosanoid resolvin D2 (1 is described. The key steps involved a Wittig reaction between aldehyde 5 and the ylide derived from phosphonium salt 6 to give enyne 17 and condensation of the same ylide with aldehyde 7 to afford enyne 11. Desilylation of 11 followed by hydrozirconation and iodination gave the vinyl iodide 4 and Sonogashira coupling between this compound and enyne 3 provided alkyne 18. Acetonide deprotection, partial reduction and ester hydrolysis then gave resolvin D2 (1.

  19. Total Synthesis and the Biological Activities of (±-Norannuradhapurine

    Directory of Open Access Journals (Sweden)

    Surachai Nimgirawath

    2008-12-01

    Full Text Available The structure previously assigned to the phenolic noraporphine alkaloid, (--norannuradhapurine has been confirmed by a total synthesis of the racemic alkaloid in which the key step involved the formation of the C ring by a radical-initiated cyclization. although inactive against Staphylococcus aureus ATCC25932, Escherichia coli ATCC10536 and Candida albicans ATCC90028, (±-norannuradhapurine inhibits the production of NO, PGE2, TNF-a, IL-1b and IL-6 and the expression of iNOS and COX-2 in RAW 264.7 macrophages stimulated with LPS in vitro.

  20. Total synthesis of leopolic acid A, a natural 2,3-pyrrolidinedione with antimicrobial activity

    Science.gov (United States)

    Dhavan, Atul A; Kaduskar, Rahul D; Musso, Loana; Scaglioni, Leonardo; Martino, Piera Anna

    2016-01-01

    Summary The first total synthesis of leopolic acid A, a fungal metabolite with a rare 2,3-pyrrolidinedione nucleus linked to an ureido dipeptide, was designed and carried out. Crucial steps for the strategy include a Dieckmann cyclization to obtain the 2,3-pyrrolidinedione ring and a Wittig olefination to install the polymethylene chain. An oxazolidinone-containing leopolic acid A analogue was also synthesized. The antibacterial activity showed by both compounds suggests that they could be considered as promising candidates for future developments.

  1. A stereodivergent strategy for the preparation of corynantheine and ipecac alkaloids, their epimers, and analogues: efficient total synthesis of (-)-dihydrocorynantheol, (-)-corynantheol, (-)-protoemetinol, (-)-corynantheal, (-)-protoemetine, and related natural and nonnatural compounds.

    Science.gov (United States)

    Zhang, Wei; Bah, Juho; Wohlfarth, Andreas; Franzén, Johan

    2011-12-01

    Here we present a general and common catalytic asymmetric strategy for the total and formal synthesis of a broad number of optically active natural products from the corynantheine and ipecac alkaloid families, for example, indolo[2,3-a]- and benzo[a]quinolizidines. Construction of the core alkaloid skeletons with the correct absolute and relative stereochemistry relies on an enantioselective and diastereodivergent one-pot cascade sequence followed by an additional diastereodivergent reaction step. This allows for enantio- and diastereoselective synthesis of three out of four possible epimers of the quinolizidine alkaloids that begin from common and easily accessible starting materials by using a common synthetic route. Focus has been made on excluding protecting groups and limiting isolation and purification of synthetic intermediates. This methodology is applied in the total synthesis of the natural products (-)-dihydrocorynantheol, (-)-hirsutinol, (-)-corynantheol, (-)-protometinol, (-)-dihydrocorynantheal, (-)-corynantheal, (-)-protoemetine, (-)-(15S)-hydroxydihydrocorynantheol, and an array of their nonnatural epimers. The potential of this strategy is also demonstrated in the synthesis of biologically interesting natural product analogues not accessible through synthetic elaboration of alkaloid precursors available from nature, for example, thieno[3,2-a]quinolizidine derivatives. We also report the formal synthesis of (+)-dihydrocorynantheine, (-)-emetine, (-)-cephaeline, (-)-tubulosine, and (-)-deoxytubulosine.

  2. Microwave Assisted Synthesis of Porous NiCo2O4 Microspheres: Application as High Performance Asymmetric and Symmetric Supercapacitors with Large Areal Capacitance

    Science.gov (United States)

    Khalid, Syed; Cao, Chuanbao; Wang, Lin; Zhu, Youqi

    2016-03-01

    Large areal capacitance is essentially required to integrate the energy storage devices at the microscale electronic appliances. Energy storage devices based on metal oxides are mostly fabricated with low mass loading per unit area which demonstrated low areal capacitance. It is still a challenge to fabricate supercapacitor devices of porous metal oxides with large areal capacitance. Herein we report microwave method followed by a pyrolysis of the as-prepared precursor is used to synthesize porous nickel cobaltite microspheres. Porous NiCo2O4 microspheres are capable to deliver large areal capacitance due to their high specific surface area and small crystallite size. The facile strategy is successfully demonstrated to fabricate aqueous-based asymmetric & symmetric supercapacitor devices of porous NiCo2O4 microspheres with high mass loading of electroactive materials. The asymmetric & symmetric devices exhibit maximum areal capacitance and energy density of 380 mF cm-2 & 19.1 Wh Kg-1 and 194 mF cm-2 & 4.5 Wh Kg-1 (based on total mass loading of 6.25 & 6.0 mg) respectively at current density of 1 mA cm-2. The successful fabrication of symmetric device also indicates that NiCo2O4 can also be used as the negative electrode material for futuristic asymmetric devices.

  3. Direct and post-synthesis incorporation of chiral metallosalen catalysts into metal-organic frameworks for asymmetric organic transformations.

    Science.gov (United States)

    Xi, Weiqin; Liu, Yan; Xia, Qingchun; Li, Zijian; Cui, Yong

    2015-09-01

    Two chiral porous metal-organic frameworks (MOFs) were constructed from [VO(salen)]-derived dicarboxylate and dipyridine bridging ligands. After oxidation of V(IV) to V(V) , they were found to be highly effective, recyclable, and reusable heterogeneous catalysts for the asymmetric cyanosilylation of aldehydes with up to 95 % ee. Solvent-assisted linker exchange (SALE) treatment of the pillared-layer MOF with [Cr(salen)Cl]- or [Al(salen)Cl]-derived dipyridine ligands led to the formation of mixed-linker metallosalen-based frameworks and incorporation of [Cr(salen)] enabled its use as a heterogeneous catalyst in the asymmetric epoxide ring-opening reaction.

  4. Crystallography of Magnetite Plaquettes and their Significance as Asymmetric Catalysts for the Synthesis of Chiral Organics in Carbonaceous Chondrites

    Science.gov (United States)

    Chan, Q. H. S.; Zolensky, M. E.

    2015-01-01

    We have previously observed the magnetite plaquettes in carbonaceous chondrites using scanning electron microscope (SEM) imaging, examined the crystal orientation of the polished surfaces of magnetite plaquettes in CI Orgueil using electron backscattered diffraction (EBSD) analysis, and concluded that these magnetite plaquettes are likely naturally asymmetric materials. In this study, we expanded our EBSD observation to other magnetite plaquettes in Orgueil, and further examined the internal structure of these remarkable crystals with the use of X-ray computed microtomography.

  5. 手性辅剂樟脑磺内酰胺在不对称合成中的应用%Application of Chial Camphorsultam in Asymmetric Synthesis

    Institute of Scientific and Technical Information of China (English)

    曹秀芳; 刘盛华

    2011-01-01

    综述了手性辅剂樟脑磺内酰胺在不对称共轭加成反应、不对称Diels-Alder反应、不对称1,3-偶极环加成反应、不对称羰基化合物的a-烷基化反应、不对称羟醛缩合反应及胺化反应中的应用研究进展.%This review summarizes some application progress of camphorsultam as chiral auxiliary in asymmetric synthesis including conjugate addition, Diels-Alder reaction, 1,3-dipolar cycloaddition, α-alkylation of ketone, aldol condensation and amination reaction etc.

  6. Asymmetric synthesis of α-amino-1,3-dithianes via chiral N-phosphonyl imine-based Umpolung reaction without using chromatography and recrystallization.

    Science.gov (United States)

    Kattamuri, Padmanabha V; Ai, Teng; Pindi, Suresh; Sun, Yinwei; Gu, Peng; Shi, Min; Li, Guigen

    2011-04-15

    A series of α-amino-1,3-dithianes have been synthesized via the asymmetric Umpolung reaction of 2-lithio-1,3-dithianes with chiral N-phosphonyl imines in good chemical yields (up to 82%) and good to excellent diastereoselectivities (>99:1). The manner by which chiral N-phosphonyl imines are slowly added into the solution of 2-lithio-1,3-dithiane was found to be crucial for achieving excellent diastereoselectivity. The current synthesis was proven to follow the GAP chemistry (group-assistant-purification chemistry) process, which avoids traditional purification techniques of chromatography or recrystallization, i.e., the pure chiral α-amino-1,3-dithianes attached with the chiral N-phosphonyl group were readily obtained by washing the solid crude products with hexane or a mixture of hexane-ethyl acetate.

  7. Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases. Part 3: Michael addition reactions and miscellaneous transformations.

    Science.gov (United States)

    Aceña, José Luis; Sorochinsky, Alexander E; Soloshonok, Vadim

    2014-09-01

    The major goal of this review is a critical discussion of the literature data on asymmetric synthesis of α-amino acids via Michael addition reactions involving Ni(II)-complexes of amino acids. The material covered is divided into two conceptually different groups dealing with applications of: (a) Ni(II)-complexes of glycine as C-nucleophiles and (b) Ni(II)-complexes of dehydroalanine as Michael acceptors. The first group is significantly larger and consequently subdivided into four chapters based on the source of stereocontrolling element. Thus, a chiral auxiliary can be used as a part of nucleophilic glycine Ni(II) complex, Michael acceptor or both, leading to the conditions of matching vs. mismatching stereochemical preferences. The particular focus of the review is made on the practical aspects of the methodology under discussion and mechanistic considerations.

  8. Synthesis of derivatives of tetronic acid and pulvinic acid. Total synthesis of norbadione A; Synthese de derives de l'acide tetronique et de l'acide pulvinique. Synthese totale de la norbadione A

    Energy Technology Data Exchange (ETDEWEB)

    Mallinger, A

    2008-11-15

    When vegetables like mushrooms are contaminated by radioactive caesium 137, this radioactive caesium is associated to norbadione A, a natural pigment present in two mushroom species and which can be used as a caesium decorporation agent or maybe as protection agent against ionizing radiations. Within this perspective, this research report describes the biosynthesis and the structure and properties of the norbadione A and of pulvinic acids (physicochemical properties, anti-oxidizing properties). Then, it presents the various tetronic acids (3-acyl-, 3-alkyl-, 3-alkoxy-, 3-aryl-tetronic acids and non 3-substituted tetronic acids), their synthesis path as they are described in the literature, and presents a new synthesis approach using a tandem reaction (with different esters or hydroxy esters) and the synthesis of tetronic acids. The author also proposes a new synthesis way for methyl pulvinates, and finally reports the work on the development of a total synthesis of the norbadione A.

  9. Amine-Catalyzed Asymmetric (3 + 3) Annulations of β'-Acetoxy Allenoates: Enantioselective Synthesis of 4H-Pyrans.

    Science.gov (United States)

    Ni, Chunjie; Tong, Xiaofeng

    2016-06-29

    The asymmetric (3 + 3) annulations of β'-acetoxy allenoates with either 3-oxo-nitriles or pyrazolones have been realized by using 6'-deoxy-6'-[(l)-N,N-(2,2'-oxidiethyl)-valine amido]quinine (6h) as the catalyst. The three functions of catalyst 6h, including Lewis base (quinuclidine N), H-bond donor (amide NH), and Brønsted base (morpholine N), cooperatively take crucial roles on the chemo- and enantioselectivity, allowing for the construction of 4H-pyran and 4H-pyrano[2,3-c]pyrazole in high yields and enantioselectivity. PMID:27310820

  10. Enantiospecific Total Synthesis of the Important Biogenetic Intermediates Along the Ajmaline Pathway, (+)-Polyneuridine and (+)-Polyneuridine Aldehyde, as well as 16-Epi-Vellosimine and Macusine A

    Science.gov (United States)

    Yin, Wenyuan; Kabir, M. Shahjahan; Wang, Zhijian; Rallapalli, Sundari K.; Ma, Jun; Cook, James M.

    2011-01-01

    The first stereospecific synthesis of polyneuridine aldehyde (6), 16-epi-vellosimine (7), (+)-polyneuridine (8), and (+)-macusine A (9) has been accomplished from commercially available D-(+)-tryptophan methyl ester. D-(+)-Tryptophan has served here both as the chiral auxiliary and the starting material for the synthesis of the common intermediate, (+)-vellosimine (13). This alkaloid was available in enantiospecific fashion in seven reaction vessels in 27% overall yield from D-(+)-trytophan methyl ester (14) via a combination of the asymmetric Pictet-Spengler reaction, Dieckmann cyclization, and a stereocontrolled intramolecular enolate-driven palladium-mediated cross-coupling reaction. A new process for this stereocontrolled intramolecular cross-coupling has been developed via a copper-mediated process. The initial results of this investigation indicated that an enolate driven palladium-mediated cross-coupling reaction can be accomplished by a copper-mediated process which is less expensive and much easier to work-up. An enantiospecific total synthesis of (+)-polyneuridine aldehyde (6), which has been proposed as an important biogenetic intermediate in the biosynthesis of quebrachidine (2), was then accomplished in an overall yield of 14.1% in 13 reaction vessels from D-(+)-tryptophan methyl ester (14). Aldehyde 13 was protected as the Na-Boc aldehyde 32 and then converted into the prochiral C (16)-quaternary diol 12 via the practical Tollens’ reaction and deprotection. The DDQ-mediated oxidative cyclization and TFA/Et3SiH reductive cleavage served as protection/deprotection steps to provide a versatile entry into the three alkaloids, polyneuridine aldehyde (6), polyneuridine (8) and macusine A (9) from the quarternary diol 12. The oxidation of the 16-hydroxymethyl group present in the axial position was achieved with the Corey-Kim reagent to provide the desired β-axial aldehydes, polyneuridine aldehyde (6) and 16-epi-vellosimine (7) with 100

  11. Enantiospecific total synthesis of the important biogenetic intermediates along the ajmaline pathway, (+)-polyneuridine and (+)-polyneuridine aldehyde, as well as 16-epivellosimine and macusine A.

    Science.gov (United States)

    Yin, Wenyuan; Kabir, M Shahjahan; Wang, Zhijian; Rallapalli, Sundari K; Ma, Jun; Cook, James M

    2010-05-21

    The first stereospecific synthesis of polyneuridine aldehyde (6), 16-epivellosimine (7), (+)-polyneuridine (8), and (+)-macusine A (9) has been accomplished from commercially available d-(+)-tryptophan methyl ester. d-(+)-Tryptophan has served here both as the chiral auxiliary and the starting material for the synthesis of the common intermediate, (+)-vellosimine (13). This alkaloid was available in enantiospecific fashion in seven reaction vessels in 27% overall yield from d-(+)-trytophan methyl ester (14) via a combination of the asymmetric Pictet-Spengler reaction, Dieckmann cyclization, and a stereocontrolled intramolecular enolate-driven palladium-mediated cross-coupling reaction. A new process for this stereocontrolled intramolecular cross-coupling has been developed via a copper-mediated process. The initial results of this investigation indicated that an enolate-driven palladium-mediated cross-coupling reaction can be accomplished by a copper-mediated process which is less expensive and much easier to work up. An enantiospecific total synthesis of (+)-polyneuridine aldehyde (6), which has been proposed as an important biogenetic intermediate in the biosynthesis of quebrachidine (2), was then accomplished in an overall yield of 14.1% in 13 reaction vessels from d-(+)-tryptophan methyl ester (14). Aldehyde 13 was protected as the N(a)-Boc aldehyde 32 and then converted into the prochiral C(16)-quaternary diol 12 via the practical Tollens' reaction and deprotection. The DDQ-mediated oxidative cyclization and TFA/Et(3)SiH reductive cleavage served as protection/deprotection steps to provide a versatile entry into the three alkaloids polyneuridine aldehyde (6), polyneuridine (8), and macusine A (9) from the quarternary diol 12. The oxidation of the 16-hydroxymethyl group present in the axial position was achieved with the Corey-Kim reagent to provide the desired beta-axial aldehydes, polyneuridine aldehyde (6), and 16-epivellosimine (7) with 100

  12. Decision-making regarding total knee replacement surgery: A qualitative meta-synthesis

    Directory of Open Access Journals (Sweden)

    Ong Bie

    2007-04-01

    Full Text Available Abstract Background Knee osteoarthritis is a highly prevalent condition that can result in disability and reduced quality of life. The evidence suggests that total knee replacement surgery (TKR is an effective intervention for patients with severe knee problems, but there is also an unmet need for this treatment in the UK. To help understand the reason for this unmet need, the aim of this study was to explore the factors that influence the decision-making process of TKR surgery by synthesising the available evidence from qualitative research on this topic. Methods A meta-synthesis was undertaken. This involved sevens steps: getting started, deciding what is relevant to the initial interest, reading the studies, determining how the studies are related, translating the studies into one another, synthesising translations, and finally, expressing the synthesis. Second-order and third-order interpretations regarding decision-making in TKR surgery were drawn from the literature. Results Ten qualitative studies were found and are included in the synthesis. The evidence suggests that social and cultural categories of aging have shaped the expectation of knee osteoarthritis, and this in turn shapes patients' expectations of treatment options. The role of the health care professional was the strongest theme to emerge across all ten studies. Coping strategies and life context determine short and longer-term outcomes of TKR. Conclusion The decision-making process regarding TKR surgery is extremely complex, as patients have weigh up numerous considerations before they can make a decision about surgery. By synthesising ten qualitative studies, we have illuminated the importance of the health care professional during this process.

  13. Total Synthesis of Flocoumafen via Knoevenagel Condensation and Intramolecular Ring Cyclization: General Access to Natural Products

    Directory of Open Access Journals (Sweden)

    Mankil Jung

    2012-02-01

    Full Text Available The total synthesis and structure determination of cis- and trans-flocoumafen was described. The key synthetic steps involve Knoevenagel condensation with p-methoxybenzaldehyde, in situ decarboxylation and intramolecular ring cyclization to construct the tetralone skeleton. Stereospecific reduction of the O-alkylated ketone 13 afforded good yield of precusor alcohol 5. Final coupling of alcohol 5 with 4-hydroxy-coumarin yielded flocoumafen (1. Separation and structure determination of cis- and trans-flocoumafen through 2D NMR analyses-assisted computer simulation techniques for the evaluation of anticoagulant activities are reported for the first time. This method is useful for generating the core tetralone skeleton of 4-hydroxycoumarin derivatives and provides a generalized access to various warfarin type anticoagulants.

  14. Total Synthesis and Antifungal Activity of Palmarumycin CP17 and Its Methoxy Analogues.

    Science.gov (United States)

    Wang, Ruina; Liu, Guoyue; Yang, Mingyan; Wang, Mingan; Zhou, Ligang

    2016-01-01

    Total synthesis of naturally occurring spirobisnaphthalene palmarumycin CP17 and its methoxy analogues was first achieved through Friedel-Crafts acylation, Wolff-Kishner reduction, intramolecular cyclization, ketalization, benzylic oxidation, and demethylation using the inexpensive and readily available methoxybenzene, 1,2-dimethoxybenzene and 1,4-dimethoxybenzene and 1,8-dihydroxynaphthalene as raw materials. Demethylation with (CH₃)₃SiI at ambient temperature resulted in ring A aromatization and acetal cleavage to give rise to binaphthyl ethers. The antifungal activities of these spirobisnaphthalene derivatives were evaluated, and the results revealed that 5 and 9b exhibit EC50 values of 9.34 µg/mL and 12.35 µg/mL, respectively, against P. piricola. PMID:27164077

  15. Total Synthesis and Antifungal Activity of Palmarumycin CP17 and Its Methoxy Analogues

    Directory of Open Access Journals (Sweden)

    Ruina Wang

    2016-05-01

    Full Text Available Total synthesis of naturally occurring spirobisnaphthalene palmarumycin CP17 and its methoxy analogues was first achieved through Friedel-Crafts acylation, Wolff-Kishner reduction, intramolecular cyclization, ketalization, benzylic oxidation, and demethylation using the inexpensive and readily available methoxybenzene, 1,2-dimethoxybenzene and 1,4-dimethoxybenzene and 1,8-dihydroxynaphthalene as raw materials. Demethylation with (CH33SiI at ambient temperature resulted in ring A aromatization and acetal cleavage to give rise to binaphthyl ethers. The antifungal activities of these spirobisnaphthalene derivatives were evaluated, and the results revealed that 5 and 9b exhibit EC50 values of 9.34 µg/mL and 12.35 µg/mL, respectively, against P. piricola.

  16. Total Synthesis and Anti-Viral Activities of an Extract of Radix isatidis

    Directory of Open Access Journals (Sweden)

    Li-Wei He

    2014-12-01

    Full Text Available Radix isatidis (Banlangen, a famous traditional Chinese medicine, has been used for thousands of years in China due to its anti-viral activity. Through our research, we inferred that the anti-viral activity of Radix isatidis depended on the water-soluble part. Among the components of this extract, the isoquinoline derivative 1 was isolated for the first time and has shown better anti-viral activity than other constituents. In this study, to solve the problem of sourcing sufficient quantities of compound 1, a total synthesis route is described, and several analogues are also evaluated for their anti-viral activities. Among them, compound 8 shown potent anti-viral activity with an IC50 value of 15.3 µg/mL. The results suggested that isoquinoline derivatives possessed potent anti-viral activity and are worthy further development.

  17. Stereoselective Total Synthesis of Atractylodemayne A, a Conjugated 2(E),8(Z),10(E)-Triene-4,6-diyne.

    Science.gov (United States)

    Schmidt, Bernd; Audörsch, Stephan

    2016-03-01

    The first total synthesis of the polyacetylene natural product atractylodemayne A is reported. Stereoselective construction of the conjugated 8(Z),10(E)-diene moiety was achieved through a tethered ring-closing metathesis approach, comprising a Ru-catalyzed RCM followed by a base-induced elimination. A Pd-catalyzed Cadiot-Chodkiewicz coupling was used for the synthesis of the diyne. Overall, atractylodemayne A was synthesized in nine steps for the longest linear sequence. PMID:26886865

  18. Peloruside B, a Potent Antitumor Macrolide from the New Zealand Marine Sponge Mycale hentscheli: Isolation, Structure, Total Synthesis and Bioactivity

    OpenAIRE

    Singh, A. Jonathan; Xu, Chun-Xiao; Xu, Xiaoming; West, Lyndon M.; Wilmes, Anja; Chan, Ariane; Hamel, Ernest; John H Miller; Peter T. Northcote; Ghosh, Arun K.

    2010-01-01

    Peloruside B (2), a natural congener of peloruside A (1), was isolated in sub-milligram quantities from the New Zealand marine sponge Mycale hentscheli. Peloruside B promotes microtubule polymerization and arrests cells in the G2M phase of mitosis similar to paclitaxel, and its bioactivity was comparable to that of peloruside A. NMR-directed isolation, structure elucidation, structure confirmation by total synthesis and bioactivity of peloruside B are described in this article. The synthesis ...

  19. Total synthesis and structural revision of vannusals A and B: synthesis of the originally assigned structure of vannusal B.

    Science.gov (United States)

    Nicolaou, K C; Ortiz, Adrian; Zhang, Hongjun; Dagneau, Philippe; Lanver, Andreas; Jennings, Michael P; Arseniyadis, Stellios; Faraoni, Raffaella; Lizos, Dimitrios E

    2010-05-26

    The total synthesis of the originally assigned structure of vannusal B (2) and its diastereomer (d-2) are described. Initial forays into these structures with model systems revealed the viability of a metathesis-based approach and a SmI(2)-mediated strategy for the key cyclization to forge the central region of the molecule, ring C. The former approach was abandoned in favor of the latter when more functionalized substrates failed to enter the cyclization process. The successful, devised convergent strategy based on the SmI(2)-mediated ring closure utilized vinyl iodide (-)-26 and aldehyde fragment (+/-)-86 as key building blocks, whose lithium-mediated coupling led to isomeric coupling products (+)-87 and (-)-88 (as shown in Scheme 17 in the article). Intermediate (-)-88 was converted, via (-)-89 and (-)-90/(+)-91, to vannusal B structure 2 (as shown in Scheme 18 in the article), whose spectroscopic data did not match those reported for the natural product. Similarly, intermediate (+)-25, obtained through coupling of vinyl iodide (-)-26 and aldehyde (+/-)-27 (as shown in Scheme 13 in the article) was transformed via intermediates (-)-97 and (+)-98 (as shown in Scheme 19 in the article) to diastereomeric vannusal B structure (+)-d-2 (as shown in Scheme 19 in the article) which was also proven spectroscopically to be non-identical to the naturally occurring substance. These investigations led to the discovery and development of a number of new synthetic technologies that set the stage for the solution of the vannusal structural conundrum. PMID:20443561

  20. Enantioselective organocatalytic formal [3 + 3]-cycloaddition of alpha,beta-unsaturated aldehydes and application to the asymmetric synthesis of (-)-isopulegol hydrate and (-)-cubebaol.

    Science.gov (United States)

    Hong, Bor-Cherng; Wu, Ming-Fun; Tseng, Hsing-Chang; Liao, Ju-Hsiou

    2006-05-25

    [reaction: see text] The first highly enantioselective organocatalyzed carbo [3 + 3] cascade cycloaddition of alpha,beta-unsaturated aldehydes is reported. Using this methodology, crotonaldehyde is converted to 6-hydroxy-4-methylcyclohex-1-enecarbaldehyde, which is used in the synthesis of (-)-isopulegol hydrate, (-)-cubebaol, and p-tolualdehyde as well as (-)-6-hydroxy-4-methyl-1-cyclohexene-1-methanol acetate, an intermediate in the total synthesis of lycopodium alkaloid magellanine. Other alpha,beta-unsaturated aldehydes give rise to chiral cyclohexadienes via formal [4 + 2] reactions. PMID:16706490

  1. Acylation, Diastereoselective Alkylation, and Cleavage of an Oxazolidinone Chiral Auxiliary: A Multistep Asymmetric Synthesis Experiment for Advanced Undergraduates

    Science.gov (United States)

    Smith, Thomas E.; Richardson, David P.; Truran, George A.; Belecki, Katherine; Onishi, Megumi

    2008-01-01

    An introduction to the concepts and experimental techniques of diastereoselective synthesis using a chiral auxiliary is described. The 4-benzyl-2-oxazolidinone chiral auxiliary developed by Evans is acylated with propionic anhydride under mild conditions using DMAP as an acyl transfer catalyst. Deprotonation with NaN(TMS)[subscript 2] at -78…

  2. Design, Synthesis and Antitumor Activity of Asymmetric Bis(s-triazole Schiff-base)s Bearing Functionalized Side-Chain

    Institute of Scientific and Technical Information of China (English)

    HU,Guo-Oiang; HOU,Li-Li; XIE,Song-Oiang; HUANG,Wen-Long

    2008-01-01

    1-Amino-2-pyrid-3-yl-5-(2-benzoylethylthio)-s-triazole (1) was condensed with 1-amino-3-mercapto-5-[(un)substituted phenyl]-s-triazoles and subsequently substituted with chloroacetic acid to afford bis-s-triazole sulfanylacetic acid mono-Schiff bases (3a-3e),which were condensed with 9-formylanthracene to produce asymmetric bis(s-triazole Schiff base) sulfanylacetic acids (4a-4e).The structures of new synthesized compounds were characterized by elemental analysis and spectral data,and their in vitro antitumor activity against L1210,CHO and HL60 cell lines was evaluted via the respective IC50 values by methylthiazole trazolium (MTT) assay.

  3. Total synthesis, structural, and biological evaluation of stylissatin A and related analogs.

    Science.gov (United States)

    Shaheen, Farzana; Jabeen, Almas; Ashraf, Samreen; Nadeem-Ul-Haque, Muhammad; Shah, Zafar Ali; Ziaee, Muhammad Asad; Dastagir, Nida; Ganesan, A

    2016-09-01

    The natural product cyclic peptide stylissatin A (1a) was reported to inhibit nitric oxide production in LPS-stimulated murine macrophage RAW 264.7 cells. In the current study, solid-phase total synthesis of stylissatin A was performed by using a safety-catch linker and yielded the peptide with a trans-Phe(7) -Pro(6) linkage, whereas the natural product is the cis rotamer at this position as evidenced by a marked difference in NMR chemical shifts. In order to preclude the possibility of 1b being an epimer of the natural product, we repeated the synthesis using d-allo-Ile in place of l-Ile and a different site for macrocyclization. The resulting product (d-allo-Ile(2) )-stylissatin A (1c) was also found to have the trans-Phe(7) -Pro(6) peptide conformations like rotamer 1b. Applying the second route to the synthesis of stylissatin A itself, we obtained stylissatin A natural rotamer 1a accompanied by rotamer 1b as the major product. Rotamers 1a, 1b, and the epimer 1c were separable by HPLC, and 1a was found to match the natural product in structure and biological activity. Six related analogs 2-7 of stylissatin A were synthesized on Wang resin and characterized by spectral analysis. The natural product (1a), the rotamer (1b), and (d-allo-Ile(2) )-stylissatin A (1c) exhibited significant inhibition of NO(.) . Further investigations were focused on 1b, which also inhibited proliferation of T-cells and inflammatory cytokine IL-2 production. The analogs 2-7 weakly inhibited NO(.) production, but strongly inhibited IL-2 cytokine production compared with synthetic peptide 1b. All analogs inhibited the proliferation of T-cells, with analog 7 having the strongest effect. In the analogs, the Pro(6) residue was replaced by Glu/Ala, and the SAR indicates that the nature of this residue plays a role in the biological function of these peptides. Copyright © 2016 European Peptide Society and John Wiley & Sons, Ltd. PMID:27526945

  4. One-pot multiple reactions: asymmetric synthesis of 2,6-cis-disubstituted piperidine alkaloids from chiral aziridine.

    Science.gov (United States)

    Yadav, Nagendra Nath; Choi, Jihye; Ha, Hyun-Joon

    2016-07-01

    A divergent, new, and highly stereoselective synthesis of cis-2,6-disubstituted piperidine natural products including isosolenopsins, deoxocassine, and spectaline was achieved from chiral aziridine decorated with appropriate alkyl chains for isosolenopsins or alkynyl groups for deoxocassine and spectaline at C2. The characteristic feature of this synthesis is one-pot sequential reactions under atmospheric hydrogen including the reduction of alkyne (for deoxocassine and spectaline), reductive ring-opening of aziridine, debenzylation, and intramolecular reductive amination in high yields. The prerequisite aziridines were elaborated from commercially available (2S)-hydroxymethylaziridine through oxidation, Wittig olefination, and the Grignard reaction for isosolenopsins or substrate-controlled lithium alkynylate addition for deoxocassine and spectaline. PMID:27189444

  5. Total synthesis and in vitro bioevaluation of clavaminols A, C, H & deacetyl clavaminol H as potential chemotherapeutic and antibiofilm agents.

    Science.gov (United States)

    Vijai Kumar Reddy, T; Jyotsna, A; Prabhavathi Devi, B L A; Prasad, R B N; Poornachandra, Y; Ganesh Kumar, C

    2016-09-14

    A highly concise and expedient total synthesis of bioactive clavaminols (1-4) has been executed using commercially available achiral compound decanol. The synthetic strategy relied on trans-Wittig olefination, Sharpless asymmetric epoxidation, regioselective azidolysis and in situ detosylation followed by reduction as key reactions with good overall yield. Based on biological evaluation studies of all the synthesized compounds, it was observed that the clavaminol A (1) exhibited good cytotoxicity against DU145 and SKOV3 cell lines with IC50 value of 10.8 and 12.5 μM, respectively. Clavaminol A (1) and deacetyl clavaminol H (3) displayed selective promising inhibition towards Gram-positive pathogenic bacterial strains and showed good antifungal activity against the tested Candida strains. In addition, compounds 1 and 3 have demonstrated significant bactericidal activity. Compound 3 was found to be equipotent to the standard drug Miconazole displaying MFC value of 15.6 μg/mL against Candida albicans MTCC 854, C. albicans MTCC 1637, C. albicans MTCC 3958 and Candida glabrata MTCC 3019. Compounds 1 and 3 were also able to inhibit the biofilm formation of Micrococcus luteus MTCC 2470 and Staphylococcus aureus MLS16 MTCC 2940. Clavaminol A (1) increased the levels of reactive oxygen species (ROS) accumulation in M. luteus MTCC 2470. PMID:27187861

  6. [Development of new methods in asymmetric reactions and their applications].

    Science.gov (United States)

    Node, Manabu

    2002-01-01

    Several novel methods using chiral reagents and biocatalysts for asymmetric reactions are described. Among those reactions, asymmetric reduction via a novel tandem Michael addition/Meerwein-Ponndorf-Verley reduction of acyclic alpha,beta-unsaturated ketones using a chiral mercapto alcohol, asymmetric synthesis of allene-1,3-dicarboxylate via crystallization induced asymmetric transformation, and improved asymmetric nitroolefination of lactones and lactames at alpha-carbon using new chiral reagents were developed. In the reactions using biocatalysts, asymmetric dealkoxycarbonylation of bicyclic beta-keto diesters having sigma-symmetry with lipase or esterase to give optically active beta-keto esters, the asymmetric reduction of bicyclic 1,3-diketones having sigma-symmetry with Baker's yeast to give optically active keto alcohols, and the asymmetric aldol reaction of glycine with threonine aldolase were also developed. The above mentioned products were effectively utilized as chiral building blocks for the asymmetric synthesis of natural products and drugs.

  7. Synthesis, characterization and thermal study of some transition metal complexes of an asymmetrical tetradentate Schiff base ligand

    Directory of Open Access Journals (Sweden)

    ACHUT S. MUNDE

    2010-03-01

    Full Text Available Complexes of Cu(II, Ni(II, Co(II, Mn(II and Fe(III with an asymmetric tetradentate Schiff base ligand derived from dehydroacetic acid, 4-methyl-o-phenylenediamine and salicylic aldehyde were synthesized and characterized by elemental analysis, conductometry, magnetic susceptibility, UV–Vis, IR, 1H-NMR spectroscopy, X-ray diffraction analysis of powdered samples and thermal analysis, and screened for antimicrobial activity. The IR spectral data suggested that the ligand behaves as a dibasic tetadentate ligand towards the central metal ion with an ONNO donor atoms sequence. From the microanalytical data, the stoichiometry of the complexes 1:1 (metal:ligand was found. The physico-chemical data suggested square planar geometry for the Cu(II and Ni(II complexes and octahedral geometry for the Co(II, Mn(II and Fe(III complexes. The thermal behaviour (TGA/DTA of the complexes was studied and kinetic parameters were determined by Horowitz–Metzger and Coats–Redfern methods. The powder X-ray diffraction data suggested a monoclinic crystal system for the Co(II, Mn(II and Fe(III complexes. The ligand and their metal complexes were screened for antibacterial activity against Staphylococcus aureus and Escherichia coli and fungicidal activity against Aspergillus niger and Trichoderma viride.

  8. 1: Mass asymmetric fission barriers for {sup 98}Mo; 2: Synthesis and characterization of actinide-specific chelating agents

    Energy Technology Data Exchange (ETDEWEB)

    Veeck, A.C. [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry]|[Lawrence Livermore National Lab., CA (United States). Glenn T. Seaborg Inst. for Transactinium Science]|[Lawrence Berkeley National Lab., CA (United States). Nuclear Science Div.

    1996-08-01

    Excitation functions have been measured for complex fragment emission from the compound nucleus {sup 98}Mo, produced by the reaction of {sup 86}Kr with {sup 12}C. Mass asymmetric fission barriers have been obtained by fitting the excitation functions with a transition state formalism. The extracted barriers are {approximately} 5.7 MeV higher, on average, than the calculations of the Rotating Finite Range Model (RFRM). These data clearly show an isospin dependence of the conditional barriers when compared with the extracted barriers from {sup 90}Mo and {sup 94}Mo. Eleven different liquid/liquid extractants were synthesized based upon the chelating moieties 3,2-HOPO and 3,4-HOPO; additionally, two liquid/liquid extractants based upon the 1,2-HOPO chelating moiety were obtained for extraction studies. The Pu(IV) extractions, quite surprisingly, yielded results that were very different from the Fe(III) extractions. The first trend remained the same: the 1,2-HOPOs were the best extractants, followed closely by the 3,2-HOPOs, followed by the 3,4-HOPOs; but in these Pu(IV) extractions the 3,4-HOPOs performed much better than in the Fe(III) extractions. 129 refs.

  9. Synthesis of Highly Porous Poly(tert-butyl acrylate)-b-polysulfone-b-poly(tert-butyl acrylate) Asymmetric Membranes

    KAUST Repository

    Xie, Yihui

    2016-03-24

    For the first time, self-assembly and non-solvent induced phase separation was applied to polysulfone-based linear block copolymers, reaching mechanical stability much higher than other block copolymers membranes used in this method, which were mainly based on polystyrene blocks. Poly(tert-butyl acrylate)-b-polysulfone-b-poly(tert-butyl acrylate) (PtBA30k-b-PSU14k-b-PtBA30k) with a low polydispersity of 1.4 was synthesized by combining step-growth condensation and RAFT polymerization. Various advanced electron microscopies revealed that PtBA30k-b-PSU14k-b-PtBA30k assembles into worm-like cylindrical micelles in DMAc and adopts a “flower-like” arrangement with the PSU central block forming the shell. Computational modeling described the mechanism of micelle formation and morphological transition. Asymmetric nanostructured membranes were obtained with a highly porous interconnected skin layer and a sublayer with finger-like macrovoids. Ultrafiltration tests confirmed a water permeance of 555 L m-2 h-1 bar-1 with molecular weight cut-off of 28 kg/mol. PtBA segments on the membrane surface were then hydrolyzed and complexed with metals, leading to cross-linking and enhancement of antibacterial capability.

  10. 1: Mass asymmetric fission barriers for 98Mo; 2: Synthesis and characterization of actinide-specific chelating

    International Nuclear Information System (INIS)

    Excitation functions have been measured for complex fragment emission from the compound nucleus 98Mo, produced by the reaction of 86Kr with 12C. Mass asymmetric fission barriers have been obtained by fitting the excitation functions with a transition state formalism. The extracted barriers are ∼ 5.7 MeV higher, on average, than the calculations of the Rotating Finite Range Model (RFRM). These data clearly show an isospin dependence of the conditional barriers when compared with the extracted barriers from 90Mo and 94Mo. Eleven different liquid/liquid extractants were synthesized based upon the chelating moieties 3,2-HOPO and 3,4-HOPO; additionally, two liquid/liquid extractants based upon the 1,2-HOPO chelating moiety were obtained for extraction studies. The Pu(IV) extractions, quite surprisingly, yielded results that were very different from the Fe(III) extractions. The first trend remained the same: the 1,2-HOPOs were the best extractants, followed closely by the 3,2-HOPOs, followed by the 3,4-HOPOs; but in these Pu(IV) extractions the 3,4-HOPOs performed much better than in the Fe(III) extractions. 129 refs

  11. Direct asymmetric vinylogous aldol reaction of allyl ketones with isatins: Divergent synthesis of 3-hydroxy-2-oxindole derivatives

    KAUST Repository

    Zhu, Bo

    2013-05-03

    6 in 1: The highly enantioselective title reaction is mediated by a bifunctional catalyst and leads to E-configured vinylogous aldol products (see scheme). These products are used as common intermediates in the synthesis of six biologically active 3-hydroxy-2-oxindole derivatives (e.g., CPC-1). Computational studies indicated that the observed stereoselectivity is a result of favorable secondary π-π* and H-bonding interactions in the transition state. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Asymmetric synthesis of a functionalized tricyclo[6.2.0.02,6]decane ring system present in kelsoene and poduran

    Indian Academy of Sciences (India)

    Amrita Ghosh; Subrata Ghosh

    2014-11-01

    Synthesis of a functionalized tricyclo[6.2.0.02,6]decane derivative in enantiomerically pure form, the core structure present in the natural products kelsoene and poduran, is described. The key steps involve a stereocontrolled copper (I)-catalyzed intramolecular [2+2] photocycloaddition of a 1, 6-diene prepared from D-mannitol to form a substituted bicyclo[3.2.0]heptane derivative and a ring closing olefin metathesis involving the vicinal substituents on the five-membered ring of the bicyclo[3.2.0]heptane derivative.

  13. Concise synthetic approaches to naturally occurring β-hydroxyphenylarsonic: first total synthesis of papanerine, its derivative, and praecansone B

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xue; Lee, Yong Rok [Yeungnam Univ., Gyeongsan (Korea, Republic of); Kim, Sung Hong [Korea Basic Science Institute, Daegu (Korea, Republic of)

    2012-04-15

    The total synthesis of biologically interesting β-hydroxyphenylarsonic, papanerine (1), its derivative 2, praecansone B (3), and pongapinone A (4) has been accomplished starting from commercially available 2,4-dihydroxyacetophenone or 6-methoxy-2,4-dihydroxyacetophenone in 3 steps by a convergent strategy through ben zopyran formations, O-methylation, and coupling reactions.

  14. Total synthesis and structural confirmation of the marine natural product Dysinosin A: a novel inhibitor of thrombin and Factor VIIa.

    Science.gov (United States)

    Hanessian, Stephen; Margarita, Roberto; Hall, Adrian; Johnstone, Shawn; Tremblay, Martin; Parlanti, Luca

    2002-11-13

    The structure and absolute configuration of the marine antithrombotic product dysinosin A was confirmed by total synthesis. The strategy involved disconnections to three subunits, of which two were synthesized from the readily available l-glutamic acid, d-leucine, and d-mannitol. The Grubbs olefin metathesis carbocyclization reaction was utilized to prepare two intermediates. PMID:12418860

  15. A Convergent Enantioselective Total Synthesis of (-)-Perhydrohistrionicotoxin with an Intramolecular Imino Ene-type Reaction as a Key Step

    DEFF Research Database (Denmark)

    Tanner, David Ackland; Hagberg, Lars

    1998-01-01

    A convergent enantioselective total synthesis of the neurotoxic spirocyclic alkaloid (-)-perhydrohistrionicotoxin (2) is described. A Lewis acid-mediated intramolecular imine ene-type reaction was used for the key spirocyclisation step (14 to 3, with 3 being obtained as a single diastereoisomer)....

  16. A new isochroman-4-one derivative from the peel of Musa sapientum L. and its total synthesis

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    A new isochroman-4-one, 7,8-dihydroxy-3-methylisochroman-4-one was isolated from water soluble fraction of Musa sapientum L. Its structure was determined by spectroscopic evidences and its total synthesis has also been reported. The compound showed potent antihypertensive activity.

  17. First total synthesis of a guanidine alkaloid Nitensidine D using immobilized ionic liquid, microwaves and formamidinesulfinic acid

    Indian Academy of Sciences (India)

    Shallu; M L Sharma; Jasvinder Singh

    2014-11-01

    An efficient first total synthesis of a naturally occurring guanidine alkaloid, Nitensidine D isolated from ethanol extract of Pterogyne nitens has been described. Geraniol has been used as the starting material. N-alkylation of phthalimide has been achieved using immobilized ionic liquid and formamidinesulfinic acid acts as the guanylating reagent.

  18. Synthesis of transparent ZnO/PMMA nanocomposite films through free-radical copolymerization of asymmetric zinc methacrylate acetate and in-situ thermal decomposition

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Lin [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Institute of Polymers, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Li Fan, E-mail: lfan@ncu.edu.cn [Institute of Polymers, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Chen Yiwang, E-mail: ywchen@ncu.edu.cn [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Institute of Polymers, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wang Xiaofeng [Institute of Polymers, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China)

    2011-08-15

    In this paper, a new and simple approach for in-situ preparation of transparent ZnO/poly(metyl methacrylate) (ZnO/PMMA) nanocomposite films was developed. Poly(methyl methacrylate)-co-poly(zinc methacrylate acetate) (PMMA-co-PZnMAAc) copolymer was synthesized via free-radical polymerization between methyl methacrylate (MMA) and zinc methacrylate acetate (ZnMAAc), where asymmetric ZnMAAc with only one terminal double bond (C=C) was applied to act as the precursor for ZnO nanocrystals and could avoid cross-link. Subsequently, transparent ZnO/PMMA nanocomposite films were obtained by in-situ thermal decomposition. Scanning electron microscope (SEM) image revealed that ZnO nanocrystals were homogeneously dispersed in PMMA matrix. With thermal decomposition time increasing, the absorption intensity in UV region and photoluminescence intensity of ZnO/PMMA nanocomposite films enhanced. However, the optical properties diminished when the thermal decomposition temperature increased. The TGA measurement displayed ZnO/PMMA nanocomposite films prepared by the in-situ synthesis method possessed better thermal stability compared with those prepared by the physical blending method and pristine PMMA films. - Highlights: > ZnO/PMMA hybrid films were prepared via free-radical polymerization and in-situ thermal decomposition. > ZnO NCs are homogeneously dispersed in the PMMA matrix and these films have good optical properties. > Thermal stability of these films is improved compared with those of physically blending ones.

  19. Asymmetric Synthesis of (—)—1—Trimethylsiyl—ethanol with Immobilized Saccharomyces Cerevisiae Cells in Water/Organic Solvent Biphasic System

    Institute of Scientific and Technical Information of China (English)

    娄文勇; 宗敏华; 范晓丹

    2003-01-01

    Asymmetric synthesis of (-)-1-trimethylsilyl-ethanol with immobilized Saccharomyces cerevisiae cells in water/organic solvent biphasic system was studied,The effects of shake speed,hydrophobictiy of organic solvent ,volume ratio of water phase to organic phase,pH value of aqueous phase and reaction temperature on the initial reaction rate,maximum yield and enantiomeric excess(ee) of the product were systematically explored,All the above-mentioned factors had significant infuence on the reaction.n-Hexane was found to be the best organic solvent for the reaction.The optimum shake speed,volume ratio of water phase to organic phase,pH value and reaction temperature were 150 r.min-1,1/2,8 and 30℃ respectively,under which the maximum yield and enantiomeric excess of the product were as high as 96.8% and 95.7%,which are 15% and 16% higher than those of the corresponding reaction performed in aqueous phase ,To our best knowledge,this is the most satisfactory result obtained.

  20. Synthesis and spectroscopic studies of some cadmium(II) and mercury(II) complexes of an asymmetrical bidentate Schiff base ligand

    Science.gov (United States)

    Montazerozohori, Morteza; Joohari, Shiva; Musavi, Sayed Alireza

    2009-07-01

    Synthesis and spectroscopic studies on four-coordinate complexes of cadmium(II) and mercury(II) halides with a new asymmetrical bidentate Schiff base ligand of N,N'-bis[α-methylcinamaldehydene]propane-1,2-diamine(L) are described. The ligand and its complexes were characterized by elemental analysis, molar conductance, UV-visible spectra, FT-IR spectra, MS, 1H NMR and 13C NMR spectra. The complexes are non-electrolytes in DMF. The electronic spectra of the complexes were recorded in DMF solution. 1H and 13 C NMR spectra been studied in CDCl3. The molar conductance as well as spectral properties indicated the complexes do not dissociate in DMF and retain their coordination. FT-IR and NMR spectra of the complexes exhibit downfield as well as upfield shifts of the free ligand resonances that show change in geometry during the coordination. The suggested structure of the complexes is pseudo-tetrahedral. Molecular structures of the complexes have been optimized by MM+ calculations that supported pseudo-tetrahedral geometry around the metal (II) ions.

  1. Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases; Part 1: alkyl halide alkylations.

    Science.gov (United States)

    Sorochinsky, Alexander E; Aceña, José Luis; Moriwaki, Hiroki; Sato, Tatsunori; Soloshonok, Vadim A

    2013-10-01

    Alkylations of chiral or achiral Ni(II) complexes of glycine Schiff bases constitute a landmark in the development of practical methodology for asymmetric synthesis of α-amino acids. Straightforward, easy preparation as well as high reactivity of these Ni(II) complexes render them ready available and inexpensive glycine equivalents for preparing a wide variety of α-amino acids, in particular on a relatively large scale. In the case of Ni(II) complexes containing benzylproline moiety as a chiral auxiliary, their alkylation proceeds with high thermodynamically controlled diastereoselectivity. Similar type of Ni(II) complexes derived from alanine can also be used for alkylation providing convenient access to quaternary, α,α-disubstituted α-amino acids. Achiral type of Ni(II) complexes can be prepared from picolinic acid or via recently developed modular approach using simple secondary or primary amines. These Ni(II) complexes can be easily mono/bis-alkylated under homogeneous or phase-transfer catalysis conditions. Origin of diastereo-/enantioselectivity in the alkylations reactions, aspects of practicality, generality and limitations of this methodology is critically discussed.

  2. Total synthesis of the α-subunit of human glycoprotein hormones: toward fully synthetic homogeneous human follicle-stimulating hormone.

    Science.gov (United States)

    Aussedat, Baptiste; Fasching, Bernhard; Johnston, Eric; Sane, Neeraj; Nagorny, Pavel; Danishefsky, Samuel J

    2012-02-22

    Described herein is the first total chemical synthesis of the unique α-subunit of the human glycoprotein hormone (α-hGPH). Unlike the biologically derived glycoprotein hormones, which are isolated as highly complex mixtures of glycoforms, α-hGPH obtained by chemical synthesis contains discrete homogeneous glycoforms. Two such systems have been prepared. One contains the disaccharide chitobiose at the natural N-glycosylation sites. The other contains dodecamer oligosaccharides at these same sites. The dodecamer sugar is a consensus sequence incorporating the key features associated with human glycoproteins.

  3. Discovery and application of new bacterial strains for asymmetric synthesis of L-tert-butyl leucine in high enantioselectivity.

    Science.gov (United States)

    Jin, Jian-Zhong; Chang, Dong-Liang; Zhang, Jie

    2011-06-01

    Discovery of new bacterial strains with fast identification in a miniaturized system was performed for the synthesis of optically active L-tert-butyl leucine. With tert-butyl leucine amide as nitrogen source, one bacterial strain with high conversion and high enantioselectivity was discovered among 120 isolated microorganisms from local soils and identified as Mycobacterium sp. JX009. Glucose and ammonium chloride were examined as the good carbon source and nitrogen source for the cells' growth separately. The cells grew better at 30 °C and at pH 7.5 with higher activity of 2,650 U/l in comparison with other conditions. Cells' stability was improved by immobilization on synthetic resin 0730 without pretreatment. Tert-butyl leucine amide (30 mM) was successfully hydrolyzed by immobilized cells and examined as the highest chemical concentration that cells could endure. After six reaction cycles, the immobilized cells retained 90% activity with production of L-tert-butyl leucine in 98% ee. The results firstly reported the application of new bacterial strain in the hydrolysis of tert-butyl leucine amide to produce optically active L-tert-butyl leucine in an efficient way with investigation in detail. PMID:21153891

  4. An Improved Method of Total Synthesis of 2-Methoxypodocarpane-8,11,13-triene

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    12-Methoxypodocarpane-8,11,13-triene 1, the key intermediate in the synthesis of some important diterpenes, was synthesized in an efficient way, which has the characteristics of short route, simple operation and high yield.

  5. Total Synthesis of Clavosolide A via Tandem Allylic Oxidation/Oxa-Conjugate Addition Reaction

    Science.gov (United States)

    Baker, Joseph B.; Kim, Hyoungsu; Hong, Jiyong

    2015-01-01

    The tandem allylic oxidation/oxa-conjugate addition reaction promoted by the gem-disubstituent effect in conjunction with the NHC-mediated oxidative esterification was explored for the facile synthesis of clavosolide A. PMID:26236051

  6. Total Synthesis of ( - )-Kaerophyllin, ( - )-Hinokinin and (±)-Iso-hinokinin

    Institute of Scientific and Technical Information of China (English)

    夏亚穆; 梁其任; 王小龙; 曹小平; 潘鑫复

    2003-01-01

    A convenient and rapid approach for the syntheses of (-)-kaerophyllin (1), (-)-hinokinin (2) and (±)-isohinokinin (3) was described. The key steps were involved in condensation of aromatic aldehyde and alkylation of the resulting ester to give the complete skeleton of dibenzylbutyrolactone-lignan. Hydrolysis, followed by resolution with quinine, reduction and when appropriate, oxidation gave the title compound. The asynunetric total synthesis of the kaerophyllin (1) was reported for the first tlme.

  7. Total Chemical Synthesis,Assembly of Human Torque Teno Virus Genome

    Institute of Scientific and Technical Information of China (English)

    Zheng Hou; Gengfu Xiao

    2011-01-01

    Torque teno virus(TTV)is a nonenveloped virus containing a single-stranded,circular DNA genome of approximately 3.8kb.We completely synthesized the 3808 nucleotides of the TTV(SANBAN isolate)genome,which contains a hairpin structure and a GC-rich region.More than 100 overlapping oligonucleotides were chemically synthesized and assembled by polymerise chain assembly reaction(PCA),and the synthesis was completed with splicing by overlap extension(SOEing).This study establishes the methodological basis of the chemical synthesis of a viral genome for use as a live attenuated vaccine or gene therapy vector.

  8. Concise Asymmetric Synthesis and Pharmacological Characterization of All Stereoisomers of Glutamate Transporter Inhibitor TFB-TBOA and Synthesis of EAAT Photoaffinity Probes.

    Science.gov (United States)

    Leuenberger, Michele; Ritler, Andreas; Simonin, Alexandre; Hediger, Matthias A; Lochner, Martin

    2016-05-18

    Glutamate is the major excitatory neurotransmitter in the mammalian brain. Its rapid clearance after the release into the synaptic cleft is vital in order to avoid toxic effects and is ensured by several transmembrane transport proteins, so-called excitatory amino acid transporters (EAATs). Impairment of glutamate removal has been linked to several neurodegenerative diseases and EAATs have therefore received increased attention as therapeutic targets. O-Benzylated l-threo-β-hydroxyaspartate derivatives have been developed previously as highly potent inhibitors of EAATs with TFB-TBOA ((2S,3S)-2-amino-3-((3-(4-(trifluoromethyl)benzamido)benzyl)oxy)succinic acid) standing out as low-nanomolar inhibitor. We report the stereoselective synthesis of all four stereoisomers of TFB-TBOA in less than a fifth of synthetic steps than the published route. For the first time, the inhibitory activity and isoform selectivity of these TFB-TBOA enantio- and diastereomers were assessed on human glutamate transporters EAAT1-3. Furthermore, we synthesized potent photoaffinity probes based on TFB-TBOA using our novel synthetic strategy. PMID:26918289

  9. Total Synthesis and Structure-Activity Relationship of Glycoglycerolipids from Marine Organisms

    Directory of Open Access Journals (Sweden)

    Jun Zhang

    2014-06-01

    Full Text Available Glycoglycerolipids occur widely in natural products, especially in the marine species. Glycoglycerolipids have been shown to possess a variety of bioactivities. This paper will review the different methodologies and strategies for the synthesis of biological glycoglycerolipids and their analogs for bioactivity assay. In addition, the bioactivities and structure-activity relationship of the glycoglycerolipids are also briefly outlined.

  10. Total synthesis of desoxycyclomarin C and the cyclomarazines A and B.

    Science.gov (United States)

    Barbie, Philipp; Kazmaier, Uli

    2016-07-01

    Removing the β-hydroxy group from the prenylated tryptophan moiety of cyclomarins simplifies the synthesis of these interesting natural products significantly, without having a noteworthy effect on the anti-tuberculosis activity of the cyclomarins. In contrast, cyclomarazines did not show biological activity. PMID:27241664

  11. Biosynthesis and Total Synthesis Studies on The Jadomycin Family of Natural Products

    OpenAIRE

    Sharif, Ehesan U.; O’Doherty, George A.

    2012-01-01

    Jadomycins are unique angucycline polyketides, which are produced by soil bacteria Streptomyces venezuelae under specific nutrient and environmental conditions. Their unique structural complexity and biological activities have engendered extensive study of the jadomycin class of natural compounds in terms of biological activity, biosynthesis, and synthesis.

  12. Total Synthesis of the Antimicrotubule Agent (+)-Discodermolide Using Boron-Mediated Aldol Reactions of Chiral Ketones.

    Science.gov (United States)

    Paterson; Florence; Gerlach; Scott

    2000-01-01

    With a similar mechanism of action to taxol, the title compound 1 is a particularly promising candidate for development in cancer chemotherapy. This efficient synthesis, based on stereocontrolled aldol reactions, should help to overcome the scarce natural supply of 1 from the rare sponge source.

  13. Asymmetric collider

    International Nuclear Information System (INIS)

    The study of CP violation in beauty decay is one of the key challenges facing high energy physics. Much work has not yielded a definitive answer how this study might best be performed. However, one clear conclusion is that new accelerator facilities are needed. Proposals include experiments at asymmetric electron-positron colliders and in fixed-target and collider modes at LHC and SSC. Fixed-target and collider experiments at existing accelerators, while they might succeed in a first observation of the effect, will not be adequate to study it thoroughly. Giomataris has emphasized the potential of a new approach to the study of beauty CP violation: the asymmetric proton collider. Such a collider might be realized by the construction of a small storage ring intersecting an existing or soon-to-exist large synchrotron, or by arranging collisions between a large synchrotron and its injector. An experiment at such a collider can combine the advantages of fixed-target-like spectrometer geometry, facilitating triggering, particle identification and the instrumentation of a large acceptance, while the increased √s can provide a factor > 100 increase in beauty-production cross section compared to Tevatron or HERA fixed-target. Beams crossing at a non-zero angle can provide a small interaction region, permitting a first-level decay-vertex trigger to be implemented. To achieve large √s with a large Lorentz boost and high luminosity, the most favorable venue is the high-energy booster (HEB) at the SSC Laboratory, though the CERN SPS and Fermilab Tevatron are also worth considering

  14. Total Synthesis of Two 4, 5-Dioxo-seco-eudesmane Sesquiterpenes

    Institute of Scientific and Technical Information of China (English)

    Li Jing FANG; Chen Xi ZHANG; Jin Chun CHEN; Guo Jun ZHENG; Yu Lin LI

    2005-01-01

    A facile synthetic route to two seco-eudesmane, 4, 5-dioxo-10-epi-4, 5-seco-γeudesmane (1) and 4, 5-dioxo-10-epi-4, 5-seco-γ-eudesmol (2) from (+)-dihydrocarvone has been described. Avoiding expensive reagents, this highly economic method especially suits for the synthesis of 4, 5-seco-eudesman-type and ophianon-type sesquiterpenes with a double bond at position 11 and 12.

  15. The Efficient and Enantiospecific Total Synthesis of Cyclopenta[b]phenanthrenes Structurally-related to Neurosteroids

    OpenAIRE

    Qian, Mingxing; Covey, Douglas F.

    2010-01-01

    We report an efficient synthesis of cyclopenta[b]phenanthrenes functionalized at C-3 and C-8 from an optically pure Hajos-Parrish ketone. The key step is a neutral alumina catalyzed Michael addition of a Hajos-Parrish ketone derivative (4) to 1,7-octadien-3-one (2) in 98% yield. This Michael addition product went through Krapcho decarbomethoxylation, aldol condensation, lithium liquid ammonia reduction, Wacker oxidation and acid catalyzed cyclization to form cyclopenta[b]phenanthrene (1a) in ...

  16. Total synthesis of the aristolochic acids, their major metabolites, and related compounds.

    Science.gov (United States)

    Attaluri, Sivaprasad; Iden, Charles R; Bonala, Radha R; Johnson, Francis

    2014-07-21

    Plants from the Aristolochia genus have been recommended for the treatment of a variety of human ailments since the time of Hippocrates. However, many species produce the highly toxic aristolochic acids (AAs), which are both nephrotoxic and carcinogenic. For the purposes of extensive biological studies, a versatile approach to the synthesis of the AAs and their major metabolites was devised based primarily on a Suzuki-Miyaura coupling reaction. The key to success lies in the preparation of a common ring-A precursor, namely, the tetrahydropyranyl ether of 2-nitromethyl-3-iodo-4,5-methylendioxybenzyl alcohol (27), which was generated in excellent yield by oxidation of the aldoxime precursor 26. Suzuki-Miyaura coupling of 27 with a variety of benzaldehyde 2-boronates was accompanied by an aldol condensation/elimination reaction to give the desired phenanthrene intermediate directly. Deprotection of the benzyl alcohol followed by two sequential oxidation steps gave the desired phenanthrene nitrocarboxylic acids. This approach was used to synthesize AAs I-IV and several other related compounds, including AA I and AA II bearing an aminopropyloxy group at position-6, which were required for further conversion to fluorescent biological probes. Further successful application of the Suzuki-Miyaura coupling reaction to the synthesis of the N-hydroxyaristolactams of AA I and AA II then allowed the synthesis of the putative, but until now elusive, N-acetoxy- and N-sulfonyloxy-aristolactam metabolites. PMID:24877584

  17. Asymmetric synthesis of (-)-renieramycin T.

    Science.gov (United States)

    Jia, Junhao; Chen, Ruijiao; Liu, Hao; Li, Xiong; Jia, Yuanliang; Chen, Xiaochuan

    2016-08-14

    (-)-Renieramycin T, an interesting tetrahydroisoquinolinequinone alkaloid with a novel renieramycin-ecteinascidin mixed framework, is synthesized from the known phenol 16 in 22 steps with 6.2% overall yield. In the convergent route, the key cyclocondensation between the isoquinoline moiety 27 and trisubstituted phenylalaninol 14 is achieved with good selectivity to furnish bistetrahydroisoquinoline 29, which permits a rapid construction of the pentacyclic framework having a fully substituted aromatic A ring. PMID:27405490

  18. Influence of the Total Gas Flow at Different Reaction Times for CVD-Graphene Synthesis on Polycrystalline Nickel

    Directory of Open Access Journals (Sweden)

    M. P. Lavin-Lopez

    2016-01-01

    Full Text Available Optimization of the total gas flow (CH4+H2 during the reaction step for different reaction times for CVD-graphene synthesis on polycrystalline nickel foil using an atmospheric pressure set-up is reported. A thickness value related to number of graphene layers in each of the synthesized samples was determined using an Excel-VBA application. This method assigned a thickness value between 1 and 1000 and provided information on the percentage of each type of graphene (monolayer, bilayer, and multilayer deposited onto the polycrystalline nickel sheet. The influence of the total gas flow during the reaction step and the reaction time was studied in detail. Optical microscopy showed that samples were covered with different types of graphene, such as multilayer, few-layer, bilayer, and monolayer graphene. The synthesis variables were optimized according to the thickness value and the results were verified by Raman spectroscopy. The best conditions were obtained with a reaction temperature of 980°C, a CH4/H2 flow rate ratio of 0.07 v/v, a reaction time of 1 minute, and a total gas flow of 80 NmL/min. In the sample obtained under the optimized conditions, 80% of the area was covered with monolayer graphene and less than 1% with multilayer graphene.

  19. Total Synthesis of Plakilactones C, B and des-Hydroxyplakilactone B by the Oxidative Cleavage of Gracilioether Furanylidenes.

    Science.gov (United States)

    Norris, Matthew D; Perkins, Michael V

    2016-08-01

    A chemoselective oxidative cleavage of synthetic gracilioether B, 11-epi-gracilioether C benzoate, and des-hydroxygracilioether C with pyridinium chlorochromate, which proceeds with loss of the furanyl acetate, has enabled total synthesis and stereochemical elucidation of the marine sponge metabolites (4R,6R)-plakilactone C, (4R,6R,9R)-plakilactone B, and (4R,6R)-des-hydroxyplakilactone B. des-Hydroxygracilioether C, the putative biosynthetic precursor to hippolachnin A, was also found to undergo a facile ene cyclization on treatment with SnCl4. PMID:27359169

  20. Reactivity umpolung in intramolecular ring closure of 3,4-disubstituted butenolides: diastereoselective total synthesis of paeonilide.

    Science.gov (United States)

    Deore, Prashant S; Argade, Narshinha P

    2013-11-15

    Remarkable reactivity reversal stratagem in 3,4-disubstituted butenolides under acidic conditions is described. Design of a suitably substituted multifunctional butenolide followed by an acid-catalyzed chemo- and diastereoselective intramolecular ring closure via the reactivity umpolung has been demonstrated to accomplish a concise total synthesis of paeonilide. Overall, the present protocol involves one-pot reduction of an α,β-unsaturated carbon-carbon double bond and intramolecular nucleophilic insertion of oxygen function at the electron-rich γ-position of butenolide. The involved mechanistic aspects have also been discussed. PMID:24175675

  1. Tanjungides A and B: New Antitumoral Bromoindole Derived Compounds from Diazona cf formosa. Isolation and Total Synthesis

    Directory of Open Access Journals (Sweden)

    Carmen Murcia

    2014-02-01

    Full Text Available Tanjungides A (1 (Z isomer and B (2 (E isomer, two novel dibrominated indole enamides, have been isolated from the tunicate Diazona cf formosa. Their structures were determined by spectroscopic methods including HRMS, and extensive 1D and 2D NMR. The stereochemistry of the cyclised cystine present in both compounds was determined by Marfey’s analysis after chemical degradation and hydrolysis. We also report the first total synthesis of these compounds using methyl 1H-indole-3-carboxylate as starting material and a linear sequence of 11 chemical steps. Tanjungides A and B exhibit significant cytotoxicity against human tumor cell lines.

  2. Tanjungides A and B: new antitumoral bromoindole derived compounds from Diazona cf formosa. isolation and total synthesis.

    Science.gov (United States)

    Murcia, Carmen; Coello, Laura; Fernández, Rogelio; Martín, María Jesús; Reyes, Fernando; Francesch, Andrés; Munt, Simon; Cuevas, Carmen

    2014-02-21

    Tanjungides A (1) (Z isomer) and B (2) (E isomer), two novel dibrominated indole enamides, have been isolated from the tunicate Diazona cf formosa. Their structures were determined by spectroscopic methods including HRMS, and extensive 1D and 2D NMR. The stereochemistry of the cyclised cystine present in both compounds was determined by Marfey's analysis after chemical degradation and hydrolysis. We also report the first total synthesis of these compounds using methyl 1H-indole-3-carboxylate as starting material and a linear sequence of 11 chemical steps. Tanjungides A and B exhibit significant cytotoxicity against human tumor cell lines.

  3. The first protein ever synthesized in vitro——a personal reminiscence of the total synthesis of crystalline insulin

    Institute of Scientific and Technical Information of China (English)

    ZHANG YouShang

    2010-01-01

    @@ The total synthesis of crystalline bovine insulin started in 1958 was fully accomplished in 1965.This formidable task was a collaboration of the Institute of Biochemistry in Shanghai, the Institute of Organic Chemistry in Shanghai and the Department of Chemistry in Beijing University.It is difficult to say exactly how many people were involved in this project, as many contributors, e.g.Director Wang YingLai and Deputy Director Cao TianQin of the Institute of Biochemistry, were not included in the author list of the published papers.

  4. Enantioselective total synthesis of (−)-epoxyquinols A and B. Novel, convenient access to chiral epoxyquinone building blocks through enzymatic desymmetrization

    OpenAIRE

    Mehta, Goverdhan; Islam, Kabirul

    2004-01-01

    Following our recent total synthesis of the biologically potent natural products epoxyquinols A and B in racemic form, we have now accomplished the total synthesis of the (−)-epoxyquinols A and B, anti-podes of the angiogenesis inhibiting natural products, through a protocol that involves enzymatic desymmetrization of a versatile epoxyquinone derivative, readily available from the Diels–Alder adduct of cyclopentadiene and p-benzoquinone.

  5. The First Total Synthesis of 4,4′-Biisofraxidin

    Institute of Scientific and Technical Information of China (English)

    LEi,Jiang-Guang(雷建光); LIN,Gu-Qiang(林国强)

    2002-01-01

    The 4,4′- biisofraxidin, isolated from balsamina L. was synthesized for the first time in the total yield of 7% by 11 steps, in which the key step was the cyclization and Ni(0)- catalyzed coupling reaction.

  6. Total synthesis and biochemical evaluation of azumamides A–E and analogs

    DEFF Research Database (Denmark)

    Villadsen, Jesper

    structures. The key step in this route is a diastereoselective Mannich reaction, which enabled us to prepare two site-specifically edited epimeric azumamide analogs, where the stereochemistry in the unique -amino acid was inverted. The two epimeric homologs were screened together with azumamide A−E against...... the entire panel of recombinant HDAC isoforms. Thus, providing the first full profiling of the azumamides. The epimers were inactive against the full panel of HDAC enzymes and show that the -amino acid scaffold is highly sensitive to modifications in the stereochemistry. The profiling of the natural products...... analogs. Having observed the importance of the aromatic amino acid in the azumamides, a tryptophan-series was also prepared. The synthesis of these compounds underline the broad perspective and flexibility of the developed Mannich strategy. The dimethylated analogs were found to be poor HDAC inhibitors...

  7. Homogeneous asymmetric catalysis in fragrance chemistry.

    Science.gov (United States)

    Ciappa, Alessandra; Bovo, Sara; Bertoldini, Matteo; Scrivanti, Alberto; Matteoli, Ugo

    2008-06-01

    Opposite enantiomers of a chiral fragrance may exhibit different olfactory activities making a synthesis in high enantiomeric purity commercially and scientifically interesting. Accordingly, the asymmetric synthesis of four chiral odorants, Fixolide, Phenoxanol, Citralis, and Citralis Nitrile, has been investigated with the aim to develop practically feasible processes. In the devised synthetic schemes, the key step that leads to the formation of the stereogenic center is the homogeneous asymmetric hydrogenation of a prochiral olefin. By an appropriate choice of the catalyst and the reaction conditions, Phenoxanol, Citralis, and Citralis Nitrile were obtained in high enantiomeric purity, and odor profiles of the single enantiomers were determined.

  8. Total synthesis of cordatanine, structural reassignment of drymaritin, and anti-inflammatory activity of synthetic precursors.

    Science.gov (United States)

    Fang, Hsin Wei; Liao, Yu-Ren; Hwang, Tsong-Long; Shieh, Po-Chuen; Lee, Kuo-Hsiung; Hung, Hsin-Yi; Wu, Tian-Shung

    2015-09-15

    In this study, cordatanine, with a canthin-6-one skeleton, was totally synthesized in four steps via a Pictet-Spengler reaction using tryptamine and methyl glyoxylate with a total yield of 8%. The NMR spectra of synthesized cordatanine compared well with those of drymaritin isolated by Hsieh et al., confirming the need to revise the original structural assignment. In addition, kumujian A, a synthetic intermediate, showed significant anti-inflammatory effects, inhibiting both superoxide anion generation (IC50 4.87 μg/mL) and elastase release (IC50 6.29 μg/mL). PMID:26248804

  9. Total Synthesis of Trimethoprim%甲氧苄啶的全合成

    Institute of Scientific and Technical Information of China (English)

    冀亚飞; 李前荣

    2001-01-01

    对甲酚为起始原料,以总收率40.6%的高收率合成了杀菌增效剂甲氧苄啶.对 甲酚进行溴化、水解反应得到4-羟基-3,5-二溴苯甲醛;该化合物以甲醇钠甲醇溶液 进行甲氧基化反应获得4-羟基-3,5-二甲氧基苯甲醛的酚钠盐,然后直接以硫酸二甲 酯进行甲基化反应得到3,4,5-三甲氧基苯甲醛;用其通过与甲醇钠、丙烯氰的甲醇溶 液反应得到肉桂氰衍生物;该衍生物先经碱催化的1,3-质子转移异构化到烯醚结构, 再与甲醇加成,直接与胍缩合环化,最终得到甲氧苄啶.%Antibacterial synergist trimethoprim was synthesized from p-cresol in an overall yield as high as 40. 6%. p-cresol was brominated and hydrolyzed to give 3, 5-dibromo-4-hydroxyben- zaldehyde, which was methoxylated by methanolic sodium methoxide associated with cuprous chloride and dimethyfformamide(DMF)as catalyst at 125℃ (ca. 0.SMPa)to provide sodium phenolate of 3,5- dimethoxy-4-hydroxybenzaldehyde, from which 3,4,5-trimethoxybenzaldehyde was obtained by methy lation directly with dimethylsuffate in aqueous sodium hydroxide. Efficient synthesis of trimethoprim from 3,4,5-trimethoxybenzaldehyde was accomplished by condensation with methanolic sodium methox ide, methanol and acrylonitrile via prior base-catalyzed 1,3-prototropic isomerization of cinnamonitrile converted into the enol ether, followed by addition with methanol at 90℃ (ca. 0.05MPa)and cyclo condensation directly with guanidine in dimethyl sulfoxide(DMSO)at 110℃ with the removal of methanol. "One-pot" method was used in the synthesis starting from economical, convenient and envi ronmental awareness.

  10. Monitoring the catalytic synthesis of glycerol carbonate by real-time attenuated total reflection FTIR spectroscopy

    NARCIS (Netherlands)

    Calvino-Casilda, V.; Mul, G.; Fernandez, J.F.; Rubio-Marcos, F.; Banares, M.A.

    2011-01-01

    In situ Attenuated Total Reflectance FTIR spectroscopy was used to study the carbonylation of glycerol with urea. Cobalt oxide nanoparticles, Co3O4, hierarchically dispersed on zinc oxide microparticles, ZnO, were used as catalysts. The present work demonstrates that in situ real-time attenuated tot

  11. Chiral N-1-adamantyl-N-trans-cinnamylaniline type ligands: synthesis and application to palladium-catalyzed asymmetric allylic alkylation of indoles.

    Science.gov (United States)

    Mino, Takashi; Nishikawa, Kenji; Asano, Moeko; Shima, Yamato; Ebisawa, Toshibumi; Yoshida, Yasushi; Sakamoto, Masami

    2016-08-21

    Such chiral phosphine-internal olefin hybrid type ligands as N-1-adamantyl-N-cinnamylaniline derivatives 1 with C(aryl)-N(amine) bond axial chirality were synthesized and utilized for the palladium-catalyzed asymmetric allylic alkylation of indoles to afford the desired products in high enantioselectivities (up to 98% ee). PMID:27425209

  12. Ethylene in Organic Synthesis. A New Route to Anticholenergic Pyrrolidinoindolines, and Other Molecules with All Carbon-Quaternary Centers via Asymmetric Hydrovinylation

    Science.gov (United States)

    Lim, Hwan Jung; RajanBabu, T. V.

    2011-01-01

    The asymmetric hydrovinylation (1 mol % Ni-cat., 1 atm, ethylene, >98% ee) products from 1-methylenetetralines are readily converted into 3,3-disubstituted oxindoles, and subsequently to pyrrolidinoindolines. These hydrovinylation products are also useful for the syntheses of enantiopure benzomorphans. PMID:22103775

  13. One-pot synthesis of CoNiO{sub 2} single-crystalline nanoparticles as high-performance electrode materials of asymmetric supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Du, Weimin, E-mail: dwmchem@163.com; Gao, Yanping; Tian, Qingqing; Li, Dan; Zhang, Zhenhu; Guo, Jiaojiao [Anyang Normal University, College of Chemistry and Chemical Engineering (China); Qian, Xuefeng [Shanghai Jiao Tong University, School of Chemistry and Chemical Technology (China)

    2015-09-15

    A facile one-pot solvothermal method has been developed to synthesize CoNiO{sub 2} single-crystalline nanoparticles. Crystal phase, morphology, crystal lattice, and composition of the obtained products were characterized by X-ray diffraction, scanning electron microscope, high-resolution transmission electron microscopy, and energy-dispersive X-ray analysis, respectively. Results revealed that the as-synthesized CoNiO{sub 2} nanoparticles belong to cubic structure with narrow size-distribution (8–10 nm). Subsequently, new asymmetric supercapacitors were successfully assembled with CoNiO{sub 2} nanoparticles as positive electrode and activated carbon as negative electrode. The electrochemical results show that asymmetric supercapacitors based on CoNiO{sub 2} nanoparticles possess excellent supercapacitor properties, i.e., a stable electrochemical window of 0–1.7 V, higher energy density of 24.0 Wh/kg at a power density of 415.4 W/kg, and excellent cycling stability (96.8 % capacitance retention after 5000 charge–discharge cycles). Meanwhile, both a light-emitting diode and a mini fan can be powered by two series connection asymmetric supercapacitors. These results imply that the present asymmetric supercapacitors based on CoNiO{sub 2} nanoparticles possess the promising potential application in the field of high-performance energy storage.

  14. Synthesis of Novel Monophosphoramidite Ligands Derived from L-Proline for Rh-catalyzed Asymmetric Hydrogenation of α-Dehydroamino Acid Esters

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    Two novel monophosphoramidites were synthesized through a five-step transformation from commercially available L-proline. In the Ph-catalyzed asymmetric hydrogenation of α-dehydroamino acid derivatives, ligand (Sc,Ra)-1b showed good enantioselectivity and up to 91% e.e. was obtained.

  15. Sol–gel auto-combustion synthesis of totally immiscible NiAg alloy

    International Nuclear Information System (INIS)

    Highlights: ► Chemically synthesized immiscible NiAg alloy nanoparticles without protecting matrix. ► A chemical method providing both a nonequilibrium thermal process and a good mixing of precursors. ► Observation of extinction planes in NiAg alloy. -- Abstract: Immiscible crystalline NiAg alloy was successfully synthesized by the newly developed sol–gel auto-combustion method. The structure and composition were examined by X-ray diffraction (XRD) and high resolution transmission electron microscope (HRTEM). All evidence supports that homogeneous NiAg alloy with FCC structure was synthesized. The differential thermal analysis and thermogravimetry (DTA–TG) measurement shows that the alloy has a good thermal stability until 315 °C. Unusually some extinction planes are observed in the XRD pattern and HRTEM images. The random distribution of atoms and the large difference between Ni and Ag atom form factors should be regarded as the main reasons for the observation of the extinction planes. The quenching like nonequilibrium thermal process in the combustion is taken as the key factor in the synthesis of immiscible alloy. And the addition of ethylene glycol in the precursors is found to benefit the formation of NiAg alloy.

  16. First Total Synthesis of Hyacinthacine A6 from the Protected Derivative of Polyhydroxylated Pyrrolidine

    Institute of Scientific and Technical Information of China (English)

    ZHANG Tao-xiang; ZHOU Ling; AO Xiao-ping

    2008-01-01

    (1S,2R,3R,5R,7aR)-1,2-Dihydroxy-3-hydroxymethy1-5-methylpyrrolizidine(hyacinthacine A6,1) was synthesized by Wittig's methodology via the reaction of aldehyde 6,prepared from the partially protected derivative of polyhydroxylatcd pyrrolidine,with appropriated ylides,followed by cyclization through the internal reductive amination process of the resulting a,β-unsaturated ketone 7,and total deprotection.

  17. Synthesis,Charactcrization and Antibacterial Property of Strontium Half and Totally Substituted Hydroxyapatite Nanoparticles

    Institute of Scientific and Technical Information of China (English)

    LIN Yingguang; YANG Zhuoru; CHENG Jiang; WANG Lianshi

    2008-01-01

    Nanoparticles of hydroxyapatite(HAP),strontium half substituted hydroxyapatite(SrCaHAP) and strontium totally substituted hydroxyapatite(SrHAP)were prepared by sol-gel-supercritical fluid drying (SCFD) method.The nanoparticles were characterized by element content analysis,FT-IR,XRD and TEM,and the effects of strontium substitution on crystal structure.crystallinity,particle shape and antibacterial propemes of the nanoparticles on Escherichia coli,Staphylococcus aureus,Lactobacillus were researched.Results show that strontium can half and totally substitute for calcium and enter the structure of apatite according to the initial atomic ratios of Sr/[Sr+Ca] as 0.5,1.The substitution decreases the IR wavenumbers of SrCaHAP and SrHAP, and changes the morphology of the nanoparticles from short rod shaped HAP to needle shaped SrCaHAE and back to short rod shaped SrHAP.The crystallinity of HAP is higher than that of SrCaHAP, but is lower thall that of SrHAP.Moreove~the antibacterial property of SrCaHAP and SrHAP are improved after the calcium is half and totally substituted by strontium.

  18. De novo asymmetric synthesis of the mezzettiaside family of natural products via the iterative use of a dual B-/Pd-catalyzed glycosylation‡

    OpenAIRE

    Bajaj, Sumit O.; Sharif, Ehesan U.; Akhmedov, Novruz G.; O'Doherty, George A.

    2014-01-01

    The first synthesis of any and all members of the mezzettiaside family of natural products has been achieved. The reported synthesis features the iterative use of the Taylor catalyst in a dual nucleophilic boron/electrophilic palladium catalyzed regioselective glycosylation. In addition, the de novo approach utilizes atomless protecting groups and the minimal use of protecting groups (2 chloroacetates for the synthesis of 10 natural products). These divergent syntheses occurred in a range of ...

  19. Efficient Total Chemical Synthesis of (13) C=(18) O Isotopomers of Human Insulin for Isotope-Edited FTIR.

    Science.gov (United States)

    Dhayalan, Balamurugan; Fitzpatrick, Ann; Mandal, Kalyaneswar; Whittaker, Jonathan; Weiss, Michael A; Tokmakoff, Andrei; Kent, Stephen B H

    2016-03-01

    Isotope-edited two-dimensional Fourier transform infrared spectroscopy (2 D FTIR) can potentially provide a unique probe of protein structure and dynamics. However, general methods for the site-specific incorporation of stable (13) C=(18) O labels into the polypeptide backbone of the protein molecule have not yet been established. Here we describe, as a prototype for the incorporation of specific arrays of isotope labels, the total chemical synthesis-via a key ester insulin intermediate-of 97 % enriched [(1-(13) C=(18) O)Phe(B24) ] human insulin: stable-isotope labeled at a single backbone amide carbonyl. The amino acid sequence as well as the positions of the disulfide bonds and the correctly folded structure were unambiguously confirmed by the X-ray crystal structure of the synthetic protein molecule. In vitro assays of the isotope labeled [(1-(13) C=(18) O)Phe(B24) ] human insulin showed that it had full insulin receptor binding activity. Linear and 2 D IR spectra revealed a distinct red-shifted amide I carbonyl band peak at 1595 cm(-1) resulting from the (1-(13) C=(18) O)Phe(B24) backbone label. This work illustrates the utility of chemical synthesis to enable the application of advanced physical methods for the elucidation of the molecular basis of protein function. PMID:26715336

  20. Asymmetric Ashes

    Science.gov (United States)

    2006-11-01

    that oscillate in certain directions. Reflection or scattering of light favours certain orientations of the electric and magnetic fields over others. This is why polarising sunglasses can filter out the glint of sunlight reflected off a pond. When light scatters through the expanding debris of a supernova, it retains information about the orientation of the scattering layers. If the supernova is spherically symmetric, all orientations will be present equally and will average out, so there will be no net polarisation. If, however, the gas shell is not round, a slight net polarisation will be imprinted on the light. This is what broad-band polarimetry can accomplish. If additional spectral information is available ('spectro-polarimetry'), one can determine whether the asymmetry is in the continuum light or in some spectral lines. In the case of the Type Ia supernovae, the astronomers found that the continuum polarisation is very small so that the overall shape of the explosion is crudely spherical. But the much larger polarization in strongly blue-shifted spectral lines evidences the presence, in the outer regions, of fast moving clumps with peculiar chemical composition. "Our study reveals that explosions of Type Ia supernovae are really three-dimensional phenomena," says Dietrich Baade. "The outer regions of the blast cloud is asymmetric, with different materials found in 'clumps', while the inner regions are smooth." "This study was possible because polarimetry could unfold its full strength thanks to the light-collecting power of the Very Large Telescope and the very precise calibration of the FORS instrument," he adds. The research team first spotted this asymmetry in 2003, as part of the same observational campaign (ESO PR 23/03 and ESO PR Photo 26/05). The new, more extensive results show that the degree of polarisation and, hence, the asphericity, correlates with the intrinsic brightness of the explosion. The brighter the supernova, the smoother, or less clumpy

  1. Extending the Glucosyl Ceramide Cassette Approach: Application in the Total Synthesis of Ganglioside GalNAc-GM1b

    Directory of Open Access Journals (Sweden)

    Miku Konishi

    2013-12-01

    Full Text Available The development of a novel cyclic glucosyl ceramide cassette acceptor for efficient glycolipid syntheses was investigated. p-Methoxybenzyl (PMB groups were selected as protecting groups at C2 and C3 of the glucose residue with the aim of improving the functionality of the cassette acceptor. The choice of the PMB group resulted in a loss of β-selectivity, which was corrected by using an appropriate tether to control the spatial arrangement and the nitrile solvent effect. To investigate the effect of linker structure on the β-selectivity of intramolecular glycosylation, several linkers for tethering the glucose and ceramide moiety were designed and prepared, namely, succinyl, glutaryl, dimethylmalonyl, and phthaloyl esters. The succinyl ester linker was the best for accessing the cassette form. The newly designed glucosyl ceramide cassette acceptor was then applied in the total synthesis of ganglioside GalNAc-GM1b.

  2. Isolation and Total Synthesis of Stolonines A-C, Unique Taurine Amides from the Australian Marine Tunicate Cnemidocarpa stolonifera.

    Science.gov (United States)

    Tran, Trong D; Pham, Ngoc B; Ekins, Merrick; Hooper, John N A; Quinn, Ronald J

    2015-07-01

    Cnemidocarpa stolonifera is an underexplored marine tunicate that only occurs on the tropical to subtropical East Coast of Australia, with only two pyridoacridine compounds reported previously. Qualitative analysis of the lead-like enhanced fractions of C. stolonifera by LC-MS dual electrospray ionization coupled with PDA and ELSD detectors led to the identification of three new natural products, stolonines A-C (1-3), belonging to the taurine amide structure class. Structures of the new compounds were determined by NMR and MS analyses and later verified by total synthesis. This is the first time that the conjugates of taurine with 3-indoleglyoxylic acid, quinoline-2-carboxylic acid and β-carboline-3-carboxylic acid present in stolonines A-C (1-3), respectively, have been reported. An immunofluorescence assay on PC3 cells indicated that compounds 1 and 3 increased cell size, induced mitochondrial texture elongation, and caused apoptosis in PC3 cells. PMID:26204949

  3. Isolation and Total Synthesis of Stolonines A-C, Unique Taurine Amides from the Australian Marine Tunicate Cnemidocarpa stolonifera.

    Science.gov (United States)

    Tran, Trong D; Pham, Ngoc B; Ekins, Merrick; Hooper, John N A; Quinn, Ronald J

    2015-07-22

    Cnemidocarpa stolonifera is an underexplored marine tunicate that only occurs on the tropical to subtropical East Coast of Australia, with only two pyridoacridine compounds reported previously. Qualitative analysis of the lead-like enhanced fractions of C. stolonifera by LC-MS dual electrospray ionization coupled with PDA and ELSD detectors led to the identification of three new natural products, stolonines A-C (1-3), belonging to the taurine amide structure class. Structures of the new compounds were determined by NMR and MS analyses and later verified by total synthesis. This is the first time that the conjugates of taurine with 3-indoleglyoxylic acid, quinoline-2-carboxylic acid and β-carboline-3-carboxylic acid present in stolonines A-C (1-3), respectively, have been reported. An immunofluorescence assay on PC3 cells indicated that compounds 1 and 3 increased cell size, induced mitochondrial texture elongation, and caused apoptosis in PC3 cells.

  4. Isolation and Total Synthesis of Stolonines A–C, Unique Taurine Amides from the Australian Marine Tunicate Cnemidocarpa stolonifera

    Directory of Open Access Journals (Sweden)

    Trong D. Tran

    2015-07-01

    Full Text Available Cnemidocarpa stolonifera is an underexplored marine tunicate that only occurs on the tropical to subtropical East Coast of Australia, with only two pyridoacridine compounds reported previously. Qualitative analysis of the lead-like enhanced fractions of C. stolonifera by LC-MS dual electrospray ionization coupled with PDA and ELSD detectors led to the identification of three new natural products, stolonines A–C (1–3, belonging to the taurine amide structure class. Structures of the new compounds were determined by NMR and MS analyses and later verified by total synthesis. This is the first time that the conjugates of taurine with 3-indoleglyoxylic acid, quinoline-2-carboxylic acid and β-carboline-3-carboxylic acid present in stolonines A–C (1–3, respectively, have been reported. An immunofluorescence assay on PC3 cells indicated that compounds 1 and 3 increased cell size, induced mitochondrial texture elongation, and caused apoptosis in PC3 cells.

  5. Total Synthesis of 4,5-Didehydroguadiscine: A Potent Melanogenesis Inhibitor from the Brazilian Medicinal Herb, Hornschuchia obliqua.

    Science.gov (United States)

    Tanabe, Genzoh; Sugano, Youta; Shirato, Miki; Sonoda, Naoki; Tsutsui, Nozomi; Morikawa, Toshio; Ninomiya, Kiyofumi; Yoshikawa, Masayuki; Muraoka, Osamu

    2015-07-24

    The first total synthesis of the 7,7-dimethylaporphinoid, 4,5-didehydroguadiscine (6), originally isolated from the stems and roots of Hornschuchia oblique (Annonaceae), was achieved by the condensation of homopiperonylamine (7) with an α,α-dimethylphenylacetic acid derivative (8) and subsequent Pschorr reaction of the resulting benzylisoquinoline intermediate (22). The reported (13)C NMR data were partially revised on the basis of the analysis of HMBC spectra measured under different conditions. The melanogenesis inhibitory activity (IC50 = 4.7 μM) of 6 was 40 times stronger than that of arbutin (174 μM), which was used as reference standard. Furthermore, 6 was the most potent natural melanogenesis inhibitor within this class of compounds. PMID:26135746

  6. Total Synthesis of Purported Cephalosporolides H and I, Penisporolide B, and Their Stereoisomers.

    Science.gov (United States)

    Wang, Jian; Tong, Rongbiao

    2016-05-20

    Development of a unified, bioinspired synthetic strategy to access four possible diastereomers of unique 2,2-dimethyl-[5,5]-spiroacetal-cis-fused-γ-lactone (Me2SAFL) is reported, featuring pyridinium chlorochromate (PCC)-promoted oxidative ring expansion of β-hydroxy cyclic ethers and dehydrative ring-contraction rearrangement of 10-membered lactones. Synthetic utility of this strategy was demonstrated by total syntheses of 12 Me2SAFLs, corresponding to the purported cephalosporolide H (CesH), cephalosporolide I (CesI), and penisporolide B (PenB) and their possible diastereomers. Comprehensive NMR data analysis suggested that the tricyclic Me2SAFL core of CesH, CesI, and PenB should be revised to the same relative (3R*, 4R*, 6S*, 9R*) configuration and that the side chains required an unknown constitutional structure revision. PMID:27137949

  7. Total Observed Organic Carbon (TOOC): A Synthesis of North American Observations

    Science.gov (United States)

    Heald, C. L.; Goldstein, A. H.; Allan, J. D.; Aiken, A. C.; Apel, E.; Atlas, E. L.; Baker, A. K.; Bates, T. S.; Beyersdorf, A. J.; Blake, D. R.; Campos, T.; Coe, H.; Crounse, J. D.; DeCarlo, P. F.; de Gouw, J. A.; Dunlea, E. J.; Flocke, F. M.; Fried, A.; Goldan, P.; Griffin, R. J.; Herndon, S. C.; Holloway, J. S.; Holzinger, R.; Jimenez, J. L.; Junkermann, W.

    2007-01-01

    Measurements of organic carbon compounds in both the gas and particle phases made upwind, over and downwind of North America are synthesized to examine the total observed organic carbon (TOOC) in the atmosphere over this region. These include measurements made aboard the NOAA WP-3 and BAe-146 aircraft, the NOAA research vessel Ronald H. Brown, and at the Thompson Farm and Chebogue Point surface sites during the summer 2004 ICARTT campaign. Both winter and summer 2002 measurements during the Pittsburgh Air Quality Study are also included. Lastly, the spring 2002 observations at Trinidad Head, CA, surface measurements made in March 2006 in Mexico City and coincidentally aboard the C-130 aircraft during the MILAGRO campaign and later during the IMPEX campaign off the northwestern United States are incorporated. Concentrations of TOOC in these datasets span more than two orders of magnitude. The daytime mean TOOC ranges from 4.0 to 456 microg C/cubic m from the cleanest site (Trinidad Head) to the most polluted (Mexico City). Organic aerosol makes up 3-17% of this mean TOOC, with highest fractions reported over the northeastern United States, where organic aerosol can comprise up to 50% of TOOC. Carbon monoxide concentrations explain 46 to 86% of the variability in TOOC, with highest TOOC/CO slopes in regions with fresh anthropogenic influence, where we also expect the highest degree of mass closure for TOOC. Correlation with isoprene, formaldehyde, methyl vinyl ketone and methacrolein also indicates that biogenic activity contributes substantially to the variability of TOOC, yet these tracers of biogenic oxidation sources do not explain the variability in organic aerosol observed over North America. We highlight the critical need to develop measurement techniques to routinely detect total gas phase VOCs, and to deploy comprehensive suites of TOOC instruments in diverse environments to quantify the ambient evolution of organic carbon from source to sink.

  8. Total observed organic carbon (TOOC in the atmosphere: a synthesis of North American observations

    Directory of Open Access Journals (Sweden)

    C. L. Heald

    2008-04-01

    Full Text Available Measurements of organic carbon compounds in both the gas and particle phases made upwind, over and downwind of North America are synthesized to examine the total observed organic carbon (TOOC in the atmosphere over this region. These include measurements made aboard the NOAA WP-3 and BAe-146 aircraft, the NOAA research vessel Ronald H. Brown, and at the Thompson Farm and Chebogue Point surface sites during the summer 2004 ICARTT campaign. Both winter and summer 2002 measurements during the Pittsburgh Air Quality Study are also included. Lastly, the spring 2002 observations at Trinidad Head, CA, surface measurements made in March 2006 in Mexico City and coincidentally aboard the C-130 aircraft during the MILAGRO campaign and later during the IMPEX campaign off the northwestern United States are incorporated. Concentrations of TOOC in these datasets span more than two orders of magnitude. The daytime mean TOOC ranges from 4.0 to 456 μgC m−3 from the cleanest site (Trinidad Head to the most polluted (Mexico City. Organic aerosol makes up 3–17% of this mean TOOC, with highest fractions reported over the northeastern United States, where organic aerosol can comprise up to 50% of TOOC. Carbon monoxide concentrations explain 46 to 86% of the variability in TOOC, with highest TOOC/CO slopes in regions with fresh anthropogenic influence, where we also expect the highest degree of mass closure for TOOC. Correlation with isoprene, formaldehyde, methyl vinyl ketone and methacrolein also indicates that biogenic activity contributes substantially to the variability of TOOC, yet these tracers of biogenic oxidation sources do not explain the variability in organic aerosol observed over North America. We highlight the critical need to develop measurement techniques to routinely detect total gas phase VOCs, and to deploy comprehensive suites of TOOC instruments in diverse environments to quantify the ambient evolution of organic carbon from source

  9. Total Observed Organic Carbon (TOOC: A synthesis of North American observations

    Directory of Open Access Journals (Sweden)

    C. L. Heald

    2007-12-01

    Full Text Available Measurements of organic carbon compounds in both the gas and particle phases measured upwind, over and downwind of North America are synthesized to examine the total observed organic carbon (TOOC over this region. These include measurements made aboard the NOAA WP-3 and BAe-146 aircraft, the NOAA research vessel Ronald H. Brown, and at the Thompson Farm and Chebogue Point surface sites during the summer 2004 ICARTT campaign. Both winter and summer 2002 measurements during the Pittsburgh Air Quality Study are also included. Lastly, the spring 2002 observations at Trinidad Head, CA, surface measurements made in March 2006 in Mexico City and coincidentally aboard the C-130 aircraft during the MILAGRO campaign and later during the IMPEX campaign off the northwestern United States are incorporated. Concentrations of TOOC in these datasets span more than two orders of magnitude. The daytime mean TOOC ranges from 4.0 to 456 μgC m−3 from the cleanest site (Trinidad Head to the most polluted (Mexico City. Organic aerosol makes up 3–17% of this mean TOOC, with highest fractions reported over the northeastern United States, where organic aerosol can comprise up to 50% of TOOC. Carbon monoxide concentrations explain 46 to 86% of the variability in TOOC, with highest TOOC/CO slopes in regions with fresh anthropogenic influence, where we also expect the highest degree of mass closure for TOOC. Correlation with isoprene, formaldehyde, methyl vinyl ketene and methacrolein also indicates that biogenic activity contributes substantially to the variability of TOOC, yet these tracers of biogenic oxidation sources do not explain the variability in organic aerosol observed over North America. We highlight the critical need to develop measurement techniques to routinely detect total gas phase VOCs, and to deploy comprehensive suites of TOOC instruments in diverse environments to quantify the ambient evolution of organic carbon from source to sink.

  10. Design and synthesis of chiral Ti-1,1'-bi-2-naphthol coordination polymers for heterogeneous catalytic asymmetric oxidation of sulfides

    Institute of Scientific and Technical Information of China (English)

    YUAN Xiao-ya; WANG Xiao-tian

    2008-01-01

    Polymer-immobilized catalysis has many advantages such as easy recovery and reuse of catalyst. We prepared three novel chiral 1,1'-bi-2-naphthol-Ti coordination polymers with properly designed ligands and Ti(OiPr)4 under mild conditions. The prepared polymers exhibited good activity and excellent enantioselectivity (over 99%ee) in catalyzing the asymmetric oxidation of sulfides. The bridge linker in the polymer and the reaction solvent noticeably affected the enantioselectivity. The chiral coordination polymer was very stable and easy to separate from catalyzed reaction systems, with no significant loss of activity or enantioselectivity after reuse for at least ten times. These findings suggest a promising type of catalysts for synthesizing the widely used sulfoxides by asymmetrically oxidizing sulfides.

  11. Asymmetric inclusion process

    Science.gov (United States)

    Reuveni, Shlomi; Eliazar, Iddo; Yechiali, Uri

    2011-10-01

    We introduce and explore the asymmetric inclusion process (ASIP), an exactly solvable bosonic counterpart of the fermionic asymmetric exclusion process (ASEP). In both processes, random events cause particles to propagate unidirectionally along a one-dimensional lattice of n sites. In the ASEP, particles are subject to exclusion interactions, whereas in the ASIP, particles are subject to inclusion interactions that coalesce them into inseparable clusters. We study the dynamics of the ASIP, derive evolution equations for the mean and probability generating function (PGF) of the sites’ occupancy vector, obtain explicit results for the above mean at steady state, and describe an iterative scheme for the computation of the PGF at steady state. We further obtain explicit results for the load distribution in steady state, with the load being the total number of particles present in all lattice sites. Finally, we address the problem of load optimization, and solve it under various criteria. The ASIP model establishes bridges between statistical physics and queueing theory as it represents a tandem array of queueing systems with (unlimited) batch service, and a tandem array of growth-collapse processes.

  12. Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases. Part 2: aldol, Mannich addition reactions, deracemization and (S) to (R) interconversion of α-amino acids.

    Science.gov (United States)

    Sorochinsky, Alexander E; Aceña, José Luis; Moriwaki, Hiroki; Sato, Tatsunori; Soloshonok, Vadim

    2013-11-01

    This review provides a comprehensive treatment of literature data dealing with asymmetric synthesis of α-amino-β-hydroxy and α,β-diamino acids via homologation of chiral Ni(II) complexes of glycine Schiff bases using aldol and Mannich-type reactions. These reactions proceed with synthetically useful chemical yields and thermodynamically controlled stereoselectivity and allow direct introduction of two stereogenic centers in a single operation with predictable stereochemical outcome. Furthermore, new application of Ni(II) complexes of α-amino acids Schiff bases for deracemization of racemic α-amino acids and (S) to (R) interconversion providing additional synthetic opportunities for preparation of enantiomerically pure α-amino acids, is also reviewed. Origin of observed diastereo-/enantioselectivity in the aldol, Mannich-type and deracemization reactions, generality and limitations of these methodologies are critically discussed.

  13. Polymer-Supported Cinchona Alkaloid-Derived Ammonium Salts as Recoverable Phase-Transfer Catalysts for the Asymmetric Synthesis of α-Amino Acids

    Directory of Open Access Journals (Sweden)

    Carmen Nájera

    2004-04-01

    Full Text Available Alkaloids such as cinchonidine, quinine and N-methylephedrine have been N-alkylated using polymeric benzyl halides or co-polymerized and then N-alkylated, thus affording a series of polymer-supported chiral ammonium salts which have been employed as phase-transfer catalysts in the asymmetric benzylation of an N-(diphenylmethyleneglycine ester. These new polymeric catalysts can be easily recovered by simple filtration after the reaction and reused. The best ee’s were achieved when Merrifield resin-anchored cinchonidinium ammonium salts were employed.

  14. 度洛西汀的不对称合成研究进展%Progresses on the Asymmetric Synthesis of Duloxetine

    Institute of Scientific and Technical Information of China (English)

    阴彩霞; 刘东志; 周雪琴; 李爱军

    2007-01-01

      盐酸度洛西汀是5-羟色氨和去甲肾上腺素再摄取抑制剂,是第三代抗抑郁药。本文综述了近年来度洛西汀的不对称合成研究的进展,并评述了其优缺点。%  As the third generation of antidepressants, duloxetine hydrochloride inhibits uptake of both serotonin and norepinephrine. Asymmetric synthetic methods of duloxetine are reviewed and their advantages and disadvantages described in this paper.

  15. Synthesis of Diphosphites from trans, trans-Spiro[4,4]nonane-1,6-diol and Their Application in Rh-catalyzed Asymmetric Hydroformylation of Styrene

    Institute of Scientific and Technical Information of China (English)

    薛松; 蒋耀忠

    2004-01-01

    Chiral diphosphite ligands were prepared by the reaction of (1R,5S,6R)-(trans, trans)-spiro[4.4]nonane-1,6-diol with chlorophosphites. The rhodium(I) complexes containing these ligands were tested in the asymmetric hydroformylation of styrene and moderate enantioselectivity (up to 49% ee) was obtained. A pair of diastereomers 5a and 5b gave the opposite configuration of the product, which implies that the sense of enantioface selection is mainly dictated by the configuration of the terminal group on the ligand.

  16. Facile template-free synthesis of vertically aligned polypyrrole nanosheets on nickel foams for flexible all-solid-state asymmetric supercapacitors

    Science.gov (United States)

    Yang, Xiangwen; Lin, Zhixing; Zheng, Jingxu; Huang, Yingjuan; Chen, Bin; Mai, Yiyong; Feng, Xinliang

    2016-04-01

    This paper reports a novel and remarkably facile approach towards vertically aligned nanosheets on three-dimensional (3D) Ni foams. Conducting polypyrrole (PPy) sheets were grown on Ni foam through the volatilization of the environmentally friendly solvent from an ethanol-water solution of pyrrole (Py), followed by the polymerization of the coated Py in ammonium persulfate (APS) solution. The PPy-decorated Ni foams and commercial activated carbon (AC) modified Ni foams were employed as the two electrodes for the assembly of flexible all-solid-state asymmetric supercapacitors. The sheet-like structure of PPy and the macroporous feature of the Ni foam, which render large electrode-electrolyte interfaces, resulted in good capacitive performance of the supercapacitors. Moreover, a high energy density of ca. 14 Wh kg-1 and a high power density of 6.2 kW kg-1 were achieved for the all-solid-state asymmetric supercapacitors due to the wide cell voltage window.This paper reports a novel and remarkably facile approach towards vertically aligned nanosheets on three-dimensional (3D) Ni foams. Conducting polypyrrole (PPy) sheets were grown on Ni foam through the volatilization of the environmentally friendly solvent from an ethanol-water solution of pyrrole (Py), followed by the polymerization of the coated Py in ammonium persulfate (APS) solution. The PPy-decorated Ni foams and commercial activated carbon (AC) modified Ni foams were employed as the two electrodes for the assembly of flexible all-solid-state asymmetric supercapacitors. The sheet-like structure of PPy and the macroporous feature of the Ni foam, which render large electrode-electrolyte interfaces, resulted in good capacitive performance of the supercapacitors. Moreover, a high energy density of ca. 14 Wh kg-1 and a high power density of 6.2 kW kg-1 were achieved for the all-solid-state asymmetric supercapacitors due to the wide cell voltage window. Electronic supplementary information (ESI) available: ESI

  17. Synthesis of oxazole, oxazoline and isoxazoline derived marine natural products: A review

    Digital Repository Service at National Institute of Oceanography (India)

    Tilvi, S.; Singh, K.S.

    by oxidative cleavage of the double bond to produce carboxylic acid 2 which was condensed (via its acid chloride) with oxazolidine 3 to give 4. Asymmetric azidation using the Evans procedure gave azide 5 in diastereomerically pure form. Conversion... pseudopterosins [24]. Total synthesis of pseudopterosin A was reported by Broka [25], while pseudopterosin E have been reported by Corey [26]. Recently, David et. al. described the total synthesis of (+)-ileabethoxazole via Iron-midiated Pauson- Khand [2...

  18. Solvent-Free Synthesis, DNA-Topoisomerase II Activity and Molecular Docking Study of New Asymmetrically N,N'-Substituted Ureas

    Directory of Open Access Journals (Sweden)

    Aurea Echevarria

    2012-11-01

    Full Text Available A new series of asymmetrically N,N'-substituted ureas 20–25 was prepared using solvent free conditions, which is an eco-friendly methodology, starting with Schiff bases derived from cinnamaldehyde and p-substituted anilines, which are subsequently submitted to reduction reactions that afford the corresponding asymmetric secondary amines. All of the intermediates were prepared using solvent free reactions, which were compared to traditional methodologies. All of the reactions required a remarkably short amount of time and provided good yields when solvent free conditions were employed compared to other methodologies. The DNA-topoisomerase II-α (topo II-α activity was evaluated in relaxation assays, which showed that all of the compounds inhibited the enzyme activity at 10 μM, except for urea 24. Furthermore, a molecular docking study indicated that the compounds 20–25 binding to the topo II-α are able to interact with the same binding site as the anticancer drug etoposide, suggesting that the ureas could inhibit the enzyme by the same mechanism of action observed for etoposide, which prevents re-ligation of the DNA strands.

  19. A second-generation total synthesis of (+)-discodermolide: the development of a practical route using solely substrate-based stereocontrol.

    Science.gov (United States)

    Paterson, Ian; Delgado, Oscar; Florence, Gordon J; Lyothier, Isabelle; O'Brien, Matthew; Scott, Jeremy P; Sereinig, Natascha

    2005-01-01

    A novel total synthesis of the complex polyketide (+)-discodermolide, a promising anticancer agent of sponge origin, has been completed in 7.8% overall yield over 24 linear steps, with 35 steps altogether. This second-generation approach was designed to rely solely on substrate control for introduction of the required stereochemistry, eliminating the use of all chiral reagents or auxiliaries. The common 1,2-anti-2,3-syn stereotriad found in each of three subunits, aldehyde 9 (C(1)-C(5)), ester 40 (C(9)-C(16)), and aldehyde 13 (C(17)-C(24)), was established via a boron-mediated aldol reaction of ethyl ketone 15 and formaldehyde, followed by hydroxyl-directed reduction to give 1,3-diol 14. Alternatively, a surrogate aldehyde 22 was employed for formaldehyde in this aldol reaction, leading to the beta-hydroxy aldehyde 20 as a common building block, corresponding to the discodermolide stereotriad. Key fragment unions were achieved by a lithium-mediated anti aldol reaction of ester 40 and aldehyde 13 under Felkin-Anh control to provide (16S,17S)-adduct 51 and a boron-mediated aldol reaction between enone 10 and aldehyde 9, exploiting unprecedented remote 1,6-stereoinduction, to give the (5S)-adduct 57.

  20. Enantioselective total synthesis of epoxyquinone natural products (−)-phyllostine, (+)-epoxydon, (+)-epiepoxydon and (−)-panepophenanthrin: access to versatile chiral building blocks through enzymatic kinetic resolution

    OpenAIRE

    Mehta, Goverdhan; Islam, Kabirul

    2004-01-01

    A new enzyme mediated protocol to access versatile chiral building blocks for the synthesis of epoxyquinone natural products is delineated. Total syntheses of (−)-phyllostine, (+)-epoxydon, (+)-epiepoxydon and (−)-panepophenanthrin have been accomplished to demonstrate the efficacy of this approach.

  1. Isolation, structure elucidation, and biomimetic total synthesis of versicolamide B and the isolation of antipodal (-)-stephacidin A and (+)-notoamide B from Aspergillus versicolor

    Science.gov (United States)

    A new prenylated indole alkaloid, versicolamide B, was isolated from cultures of Aspergillus versicolor NRRL 35600. The structure was assigned by 2D NMR data, and confirmed by a biomimetic total synthesis. Versicolamide B is the first member of the paraherquamide-stephacidin family of alkaloids fo...

  2. Total synthesis of cis-hydroazulene sesquiterpenes. Base-induced and -directed elimination and rearrangement reactions of perhydronaphthalene-1,4-diol monosulfonate esters.

    NARCIS (Netherlands)

    Jenniskens, L.H.D.

    1992-01-01

    The total synthesis of a number of cis-fused hydroazulene sesquiterpenes is described in this thesis. In this synthetic study, ample attention is paid to the mechanistic aspects of the base- induced and -directed rearrangement and elimination reactions of perhydronaphthalene-1,4-diol monosulfonate e

  3. Asymmetric catalysis with short-chain peptides.

    Science.gov (United States)

    Lewandowski, Bartosz; Wennemers, Helma

    2014-10-01

    Within this review article we describe recent developments in asymmetric catalysis with peptides. Numerous peptides have been established in the past two decades that catalyze a wide variety of transformations with high stereoselectivities and yields, as well as broad substrate scope. We highlight here catalytically active peptides, which have addressed challenges that had thus far remained elusive in asymmetric catalysis: enantioselective synthesis of atropoisomers and quaternary stereogenic centers, regioselective transformations of polyfunctional substrates, chemoselective transformations, catalysis in-flow and reactions in aqueous environments.

  4. 杀结核菌素的全合成研究%An Improved Total Synthesis of Tubercidin

    Institute of Scientific and Technical Information of China (English)

    黄海洋; 阮志忠; 胡韬; 肖强

    2014-01-01

    Tubercidin is a naturally occurring pyrrolo[2,3-d]pyrimidine nucleoside with significantly biological activities, such as anti-schistosomal, antibacterial and antitumor. An improved total synthesis of tubercidin is reported using microwave promoted Vorbrüggen glycosylation as the key step. Thus, tubercidin was synthesized in 3 steps with 74%overal yield using 6-chloro-7-bromo-pyrrolo[2,3-d]pyrimidine and 1-O-acetyl-2,3,5-O-tribenzoyl-β-D-ribose as starting materials. The applica-tion of micromave irridated one-pot reaction is also reported in the synthesis of 7-deazapurine nucleosides using potassium nonafluoro-1-butanesulfonate, trimethylsilyl chloride and silylation reagent [hexamethyldisilazane or N,O-bis(trimethyl-silyl)acetamide].%杀结核菌素是一个吡咯[2,3-d]嘧啶核苷天然产物,具有显著的抗血吸虫感染、抗菌和抗肿瘤活性。报道了以微波促进的Vorbrüggen糖基化反应为关键步骤,以6-氯-7-溴-吡咯[2,3-d]嘧啶和1-O-乙酰基-2,3,5-O-三苯甲酰基-β-D-呋喃核糖为原料,经过3步反应以74%的总收率完成了杀结核菌素的全合成。同时研究了以全氟丁基磺酸钾、三甲基氯硅烷和硅基化试剂[六甲基二硅胺烷或者N,O-双(三甲基硅基)乙酰胺]在微波加热下一锅法合成7-去氮嘌呤核苷的方法。

  5. A new method for the synthesis of α-aminoalkylidenebisphosphonates and their asymmetric phosphonyl-phosphinyl and phosphonyl-phosphinoyl analogues

    Directory of Open Access Journals (Sweden)

    Anna Kuźnik

    2015-08-01

    Full Text Available A convenient approach has been developed to α-aminoalkylidenebisphosphonates and their asymmetric phosphonyl-phosphinyl and phosphonyl-phosphinoyl analogues by α-phosphonylation, α-phosphinylation or α-phosphinoylation of 1-(N-acylaminoalkylphosphonates, that, in turn, are easily accessible from N-acyl-α-amino acids. Effective electrophilic activation of the α-position of 1-(N-acetylaminoalkylphosphonates was achieved by electrochemical α-methoxylation of these compounds in methanol, mediated with NaCl, followed by displacement of the methoxy group with triphenylphosphonium tetrafluoroborate to give hitherto unknown 1-(N-acetylamino-1-triphenylphosphoniumalkylphosphonate tetrafluoroborates. The latter compounds react smoothly with trialkyl phosphites, dialkyl phosphonites or alkyl phosphinites in the presence of Hünig’s base and methyltriphenylphosphonium iodide in a Michaelis–Arbuzov-like reaction to give the expected alkylidenebisphosphonates, 1-phosphinylalkylphosphonates or 1-phosphinoylalkylphosphonates, respectively, in good yields.

  6. Controlled synthesis, asymmetrical transport behavior and luminescence properties of lanthanide doped ZnO mushroom-like 3D hierarchical structures

    Science.gov (United States)

    Yue, Dan; Lu, Wei; Jin, Lin; Li, Chunyang; Luo, Wen; Wang, Mengnan; Wang, Zhenling; Hao, Jianhua

    2014-10-01

    Lanthanide doped ZnO mushroom-like 3D hierarchical structures have been fabricated by polyol-mediated method and characterized by various microstructural and optical techniques. The results indicate that the as-prepared ZnO:Ln3+ (Ln = Tb, Eu) samples have a hexagonal phase structure and possess a mushroom-like 3D hierarchical morphology. The length of the whole mushroom from stipe bottom to pileus top is about 1.0 μm, and the diameters of pileus and stipe are about 0.8 μm and 0.4 μm, respectively. It is found that the flow of N2 is the key parameter for the formation of the novel ZnO structure and the addition of (NH4)2HPO4 has a prominent effect on the phase structure and the growth of mushroom-like morphology. The potential mechanism of forming this morphology is proposed. The pileus of the formed mushroom is assembled by several radial ZnO:Ln3+ nanorods, whereas the stipe is composed of over layered ZnO:Ln3+ nanosheets. Moreover, asymmetrical I-V characteristic curves of ZnO:Ln3+ mushrooms indicate that the texture composition of the 3D hierarchical morphology might lead to the asymmetrical transport behavior of electrical conductivity. Lanthanide doped ZnO samples can exhibit red or green emission under the excitation of UV light.Lanthanide doped ZnO mushroom-like 3D hierarchical structures have been fabricated by polyol-mediated method and characterized by various microstructural and optical techniques. The results indicate that the as-prepared ZnO:Ln3+ (Ln = Tb, Eu) samples have a hexagonal phase structure and possess a mushroom-like 3D hierarchical morphology. The length of the whole mushroom from stipe bottom to pileus top is about 1.0 μm, and the diameters of pileus and stipe are about 0.8 μm and 0.4 μm, respectively. It is found that the flow of N2 is the key parameter for the formation of the novel ZnO structure and the addition of (NH4)2HPO4 has a prominent effect on the phase structure and the growth of mushroom-like morphology. The potential

  7. Solvothermal Synthesis of Three-Dimensional Hierarchical CuS Microspheres from a Cu-Based Ionic Liquid Precursor for High-Performance Asymmetric Supercapacitors.

    Science.gov (United States)

    Zhang, Jing; Feng, Huijie; Yang, Jiaqin; Qin, Qing; Fan, Hongmin; Wei, Caiying; Zheng, Wenjun

    2015-10-01

    It is meaningful to exploit copper sulfide materials with desired structure as well as potential application due to their cheapness and low toxicity. A low-temperature and facile solvothermal method for preparing three-dimensional (3D) hierarchical covellite (CuS) microspheres from an ionic liquid precursor [Bmim]2Cu2Cl6 (Bmim = 1-butyl-3-methylimidazolium) is reported. The formation of CuS nanostructures was achieved by decomposition of intermediate complex Cu(Tu)3Cl (thiourea = Tu), which produced CuS microspheres with diameters of 2.5-4 μm assembled by nanosheets with thicknesses of 10-15 nm. The ionic liquid, as an "all-in-one" medium, played a key role for the fabrication and self-assembly of CuS nanosheets. The alkylimidazolium rings ([Bmim](+)) were found to adsorb onto the (001) facets of CuS crystals, which inhibited the crystal growth along the [001] direction, while the alkyl chain had influence on the assembly of CuS nanosheets. The CuS microspheres showed enhanced electrochemical performance and high stability for the application in supercapacitors due to intriguing structural design and large specific surface area. When this well-defined CuS electrode was assembled into an asymmetric supercapacitor (ASC) with an activated carbon (AC) electrode, the CuS//AC-ASC demonstrated good cycle performance (∼88% capacitance after 4000 cycles) and high energy density (15.06 W h kg(-1) at a power density of 392.9 W kg(-1)). This work provides new insights into the use of copper sulfide electrode materials for asymmetric supercapacitors and other electrochemical devices. PMID:26371955

  8. Cell-sized asymmetric lipid vesicles facilitate the investigation of asymmetric membranes

    Science.gov (United States)

    Kamiya, Koki; Kawano, Ryuji; Osaki, Toshihisa; Akiyoshi, Kazunari; Takeuchi, Shoji

    2016-09-01

    Asymmetric lipid giant vesicles have been used to model the biochemical reactions in cell membranes. However, methods for producing asymmetric giant vesicles lead to the inclusion of an organic solvent layer that affects the mechanical and physical characteristics of the membrane. Here we describe the formation of asymmetric giant vesicles that include little organic solvent, and use them to investigate the dynamic responses of lipid molecules in the vesicle membrane. We formed the giant vesicles via the inhomogeneous break-up of a lipid microtube generated by applying a jet flow to an asymmetric planar lipid bilayer. The asymmetric giant vesicles showed a lipid flip-flop behaviour in the membrane, superficially similar to the lipid flip-flop activity observed in apoptotic cells. In vitro synthesis of membrane proteins into the asymmetric giant vesicles revealed that the lipid asymmetry in bilayer membranes improves the reconstitution ratio of membrane proteins. Our asymmetric giant vesicles will be useful in elucidating lipid–lipid and lipid–membrane protein interactions involved in the regulation of cellular functions.

  9. Asymmetric Synthesis and Binding Study of New Long-Chain HPA-12 Analogues as Potent Ligands of the Ceramide Transfer Protein CERT.

    Science.gov (United States)

    Ďuriš, Andrej; Daïch, Adam; Santos, Cécile; Fleury, Laurence; Ausseil, Frédéric; Rodriguez, Frédéric; Ballereau, Stéphanie; Génisson, Yves; Berkeš, Dušan

    2016-05-01

    A series of 12 analogues of the Cer transfer protein (CERT) antagonist HPA-12 with long aliphatic chains were prepared as their (1R,3S)-syn and (1R,3R)-anti stereoisomers from pivotal chiral oxoamino acids. The enantioselective access to these intermediates as well as their ensuing transformation relied on a practical crystallization-induced asymmetric transformation (CIAT) process. Sonogashira coupling followed by triple bond reduction and thiophene ring hydrodesulfurization (HDS) into the corresponding alkane moieties was then implemented to complete the synthetic routes delivering the targeted HPA-12 analogues in concise 4- to 6-step reaction sequences. Ten compounds were evaluated regarding their ability to bind to the CERT START domain by using the recently developed time-resolved FRET-based homogeneous (HTR-FRET) binding assay. The introduction of a lipophilic appendage on the phenyl moiety led to an overall 10- to 1000-fold enhancement of the protein binding, with the highest effect being observed for a n-hexyl residue in the meta position. The importance of the phenyl ring for the activity was indicated by the reduced potency of the 3-deoxyphytoceramide aliphatic analogues. The 1,3-syn stereoisomers were systematically more potent than their 1,3-anti analogues. In silico studies were used to rationalized these trends, leading to a model of protein recognition coherent with the stronger binding of (1R,3S)-syn HPAs.

  10. Asymmetric dense matter in holographic QCD

    Directory of Open Access Journals (Sweden)

    Shin Ik Jae

    2012-02-01

    Full Text Available We study asymmetric dense matter in holographic QCD.We construct asymmetric dense matter by considering two quark flavor branes with dierent quark masses in a D4/D6/D6 model. To calculate the symmetry energy in nuclear matter, we consider two quarks with equal masses and observe that the symmetry energy increases with the total charge showing the stiff dependence. This behavior is universal in the sense that the result is independent of parameters in the model. We also study strange (or hyperon matter with one light and one intermediate mass quarks. In addition to the vacuum properties of asymmetric matter, we calculate meson masses in asymmetric dense matter and discuss our results in the light of in-medium kaon masses.

  11. Pharmacophore mapping in the laulimalide series: total synthesis of a vinylogue for a late-stage metathesis diversification strategy.

    Science.gov (United States)

    Wender, Paul A; Hilinski, Michael K; Skaanderup, Philip R; Soldermann, Nicolas G; Mooberry, Susan L

    2006-08-31

    An efficient synthesis of the macrocyclic core of laulimalide with a pendant vinyl group at C20 is described, allowing for late-stage introduction of various side chains through a selective and efficient cross metathesis diversification step. Representative analogues reported herein are the first to contain modifications to only the side chain dihydropyran of laulimalide and des-epoxy laulimalide. This step-economical strategy enables the rapid synthesis of new analogues using alkenes as an inexpensive, abundantly available diversification feedstock.

  12. New phosphine-diamine and phosphine-amino-alcohol tridentate ligands for ruthenium catalysed enantioselective hydrogenation of ketones and a concise lactone synthesis enabled by asymmetric reduction of cyano-ketones

    Directory of Open Access Journals (Sweden)

    Fuentes José A

    2012-12-01

    Full Text Available Abstract Enantioselective hydrogenation of ketones is a key reaction in organic chemistry. In the past, we have attempted to deal with some unsolved challenges in this arena by introducing chiral tridentate phosphine-diamine/Ru catalysts. New catalysts and new applications are presented here, including the synthesis of phosphine-amino-alcohol P,N,OH ligands derived from (R,S-1-amino-2-indanol, (S,S-1-amino-2-indanol and a new chiral P,N,N ligand derived from (R,R-1,2-diphenylethylenediamine. Ruthenium pre-catalysts of type [RuCl2(L(DMSO] were isolated and then examined in the hydrogenation of ketones. While the new P,N,OH ligand based catalysts are poor, the new P,N,N system gives up to 98% e.e. on substrates that do not react at all with most catalysts. A preliminary attempt at realising a new delta lactone synthesis by organocatalytic Michael addition between acetophenone and acrylonitrile, followed by asymmetric hydrogenation of the nitrile functionalised ketone is challenging in part due to the Michael addition chemistry, but also since Noyori pressure hydrogenation catalysts gave massively reduced reactivity relative to their performance for other acetophenone derivatives. The Ru phosphine-diamine system allowed quantitative conversion and around 50% e.e. The product can be converted into a delta lactone by treatment with KOH with complete retention of enantiomeric excess. This approach potentially offers access to this class of chiral molecules in three steps from the extremely cheap building blocks acrylonitrile and methyl-ketones; we encourage researchers to improve on our efforts in this potentially useful but currently flawed process.

  13. Rh2 (S-1,2-NTTL)4 : A novel Rh2 (S-PTTL)4 analog with lower ligand symmetry for asymmetric synthesis of chiral cyclopropylphosphonates.

    Science.gov (United States)

    Adly, Frady G; Maddalena, Johncarlo; Ghanem, Ashraf

    2014-11-01

    A new series of dirhodium(II) tetracarboxylate was derived from N-1,2-naphthaloyl-(S)-amino acid ligands. In terms of enantioselectivity, Rh2 (S-1,2-NTTL)4 () derived from N-1,2-naphthaloyl-(S)-tert-leucine, was the best-performing catalyst among the new series in the enantioselective synthesis of cyclopropylphosphonate derivatives (up to >99% enantiomeric excess). A predictive model was proposed to justify the observed high enantiomeric induction exhibited by Rh2 (S-1,2-NTTL)4 with donor-acceptor phosphonate carbenoids.

  14. Asymmetric, Three-Component, One-Pot Synthesis of Spiropyrazolones and 2,5-Chromenediones from Aldol Condensation/NHC-Catalyzed Annulation Reactions.

    Science.gov (United States)

    Wang, Lei; Li, Sun; Chauhan, Pankaj; Hack, Daniel; Philipps, Arne R; Puttreddy, Rakesh; Rissanen, Kari; Raabe, Gerhard; Enders, Dieter

    2016-04-01

    A novel one-pot, three-component diastereo- and enantioselective synthesis of spiropyrazolones has been developed involving the aldol condensation of an enal to generate α,β-unsaturated pyrazolones, which react with a second equivalent of enal through an N-heterocyclic carbene (NHC)-catalyzed [3+2] annulation. The desired spirocyclopentane pyrazolones are obtained in moderate to good yields and good to excellent stereoselectivities. Alternatively, starting from cyclic 1,3-diketones, 2,5-chromenediones are available through [2+4] annulation. PMID:26864437

  15. Stereoselective Synthesis of Optically Active Hydrobenzoins via Asymmetric Hydrogenation of Benzils with Ru(OTf)(TsDPEN)(η6-cymene) as the Pre-catalyst%Stereoselective Synthesis of Optically Active Hydrobenzoins via Asymmetric Hydrogenation of Benzils with Ru(OTf)(TsDPEN)(η6-cymene) as the Pre-catalyst

    Institute of Scientific and Technical Information of China (English)

    黄晓飞; 李乃凯; 耿志聪; 潘锋锋; 王兴旺

    2012-01-01

    Optically active hydrobenzoins are very important building blocks for further derivation of biologically active complexes, natural products, and pharmaceutical compounds. In this paper, A practical approach has been devel- oped for asymmetric hydrogenation of benzils with Ru(OTf)(TsDPEN)(rl6-cymene) as a pre-catalyst in methanol. Therefore, a series of chiral hydrobenzoins was synthesized in good yields with good to moderate diastereoselectiv- ities and good to excellent enantioselectivities.

  16. Synthesis of the Stereoisomers of the Sex Pheromones of the Southern Corn Rootworm

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A simple and efficient asymmetric synthesis of the sex pheromone of the southern corn rootworm is discribed. The key step is the asymmetric Michael addition of enoylsultam with virtually complete asymmetric induction(e.e.%>99%)

  17. Applications of Chiral Anions in Asymmetric Catalysis

    OpenAIRE

    Hamilton, Gregory Lawrence

    2011-01-01

    The synthesis of molecules with control over their three-dimensional configuration, known as absolute stereochemistry, is one of the highest goals of synthetic organic chemists. As is so often the case, we strive to reach the facility and efficiency with which Nature achieves this goal. Fortunately, the chemist's imagination allows us to envision nearly unlimited possibilities for new modes of catalysis. In this dissertation, I discuss one branch of asymmetric catalysis that has in a short ti...

  18. Asymmetric inheritance of cytoophidia in Schizosaccharomyces pombe

    OpenAIRE

    Jing Zhang; Lydia Hulme; Ji-Long Liu

    2014-01-01

    ABSTRACT A general view is that Schizosaccharomyces pombe undergoes symmetric cell division with two daughter cells inheriting equal shares of the content from the mother cell. Here we show that CTP synthase, a metabolic enzyme responsible for the de novo synthesis of the nucleotide CTP, can form filamentous cytoophidia in the cytoplasm and nucleus of S. pombe cells. Surprisingly, we observe that both cytoplasmic and nuclear cytoophidia are asymmetrically inherited during cell division. Our t...

  19. Synthesis, characterization and crystal structure of four new asymmetric triazene ligands: An example of linear HII complex with H... secondary bonding interactions

    Indian Academy of Sciences (India)

    Mohammad Reza Melardi; Fatemeh Baber Shamsi Mogoii; Ayoob Babaii Sajirani; Jafar Attar Gharamaleki; Behrouz Notash; Mohammad Kazem Rofouei

    2015-12-01

    In this work, the asymmetric ligands [1-(phenyl)-3-(2-nitro-4-methylphenyl)]triazene (1), [1-(4-methylphenyl)-3-(2-nitro-4-methylphenyl)]triazene (2), [1-(4-ethylphenyl)-3-(2-nitro-4-methylphenyl)]triazene (3) and [1-(4-ethoxyphenyl)-3-(2-nitro-4-methylphenyl)]triazene (4), were synthesized. The reaction of the ligand (3) with HgCl2 in methanol resulted in the formation of the [HgL2] complex, (5). All compounds were characterized by means of CHN analysis, FT-IR, 1H NMR, 13C NMR spectroscopy. In addition, the crystal structures of the ligands (2) to (4) were investigated by single crystal X-ray analysis. In the solid state, all ligands exhibited trans conformation about the –N=N– double bond. The HgII complex (5) crystallized in monoclinic system with 2/ space group. The triazene ligand was found to be deprotonated prior to coordination and acts as monodentate ligand. The HgII which lies on inversion center (site symmetry $\\bar{1}$), is surrounded by two N atoms from L ligands forming a linear geometry. The other two Hg–N bonds are relatively longer and can only be regarded as weak secondary bonds. Also, Hg-3-arene -interactions are present in this compound. Hydrogen bonds, · · · and C–H· · · stacking interactions help in the stabilization of the resulted frameworks. These C–H· · · edge-to-face interactions are present with H· · · distance of 3.00 Å.

  20. Asymmetric Aldol Reaction with Formaldehyde: a Challenging Process.

    Science.gov (United States)

    Meninno, Sara; Lattanzi, Alessandra

    2016-08-01

    The asymmetric aldol reaction with formaldehyde is a fundamental carbon-carbon bond-forming reaction in organic synthesis, as well as in the quest of the origin of life, as it is thought to have been the first "molecular brick" involved in the synthetic path to complex sugars. Products of aldol reactions, i.e., the β-hydroxy carbonyl compounds, are versatile building blocks used to access a great variety of functionalised molecules. The employment of formaldehyde, as a C1 symmetric electrophile, in aldol reactions can be likely considered the most challenging, yet simplest, process to introduce a hydroxymethyl group in an asymmetric fashion. In this account, an overview of the progress achieved in the asymmetric metal- and organocatalysed aldol reaction, using readily available formalin or paraformaldehyde sources, is illustrated. Our recent contribution to this area, with the application of asymmetric hydroxymethylation in cascade processes for the synthesis of γ-butyrolactones, is also shown. PMID:27328802

  1. Improved Total Synthesis and Biological Evaluation of Potent Apratoxin S4 Based Anticancer Agents with Differential Stability and Further Enhanced Activity

    OpenAIRE

    Chen, Qi-Yin; Liu, Yanxia; Cai, Weijing; Luesch, Hendrik

    2014-01-01

    Apratoxins are cytotoxic natural products originally isolated from marine cyanobacteria that act by preventing cotranslational translocation early in the secretory pathway to downregulate receptor levels and inhibit growth factor secretion, leading to potent antiproliferative activity. Through rational design and total synthesis of an apratoxin A/E hybrid, apratoxin S4 (1a), we have previously improved the antitumor activity and tolerability in vivo. Compound 1a and newly designed analogues a...

  2. Stereoselective synthesis of (E)-beta-tributylstannyl-alpha,beta-unsaturated ketones: Construction of a key intermediate for the total synthesis of zoanthamine

    DEFF Research Database (Denmark)

    Nielsen, Thomas Eiland; Tanner, David Ackland

    2002-01-01

    (E)-beta-Trialkylstannyl-alpha,beta-unsaturated ketones are readily available from secondary propargylic alcohols via a two-step sequence involving highly regio- and stereoselective Pd(0)-catalyzed hydrostannation followed by mild oxidation (TPAP). The methodology has been applied to the synthesi...

  3. Novel poly(triphenylamine-alt-fluorene) with asymmetric hexaphenylbenzene and pyrene moieties: synthesis, fluorescence, flexible near-infrared electrochromic devices and theoretical investigation

    KAUST Repository

    Wang, Po-I.

    2016-01-13

    © The Royal Society of Chemistry 2016. In this study, a new triphenylamine-alt-fluorene conjugated copolymer, HPBPYFL6, with hexaphenylbenzene (HPB) and pyrene as asymmetrical pendant groups was synthesized via Suzuki coupling polymerization. The conjugated polymer had a weight-average molecular weight of 5.8 × 104 g mol-1 with a polydispersity index of 2.5 characterized by gel permeation chromatography (GPC). HPBPYFL6 showed good solubility in common organic solvents such as NMP, THF, toluene and dichloromethane at 25°C. In addition, HPBPYFL6 possessed a high glass transition temperature of 260°C and a 10% weight-loss temperature of 503°C in nitrogen. HPBPYFL6 bearing a pyrene moiety had a solvatochromic fluorescence shift from a green to an orange emission as the polarity of the solvent increased. Cyclic voltammetry of HPBPYFL6 films cast onto indium-tin oxide-coated glass (ITO-glass) exhibited two oxidation redox couples at an E1/2 value of 0.82 and 1.17 V versus Ag/Ag+ in an acetonitrile solution. The HPBPYFL6 film on graphene-coated PET had an E1/2 value of 0.24 and 1.12 V. Conjugated polymer films exhibited reversible electrochromic behaviour with a colour change from pale yellow to deep blue upon electrochemical oxidation and high absorbance in the near-infrared (NIR) region. The switching and bleaching times were 5.16 s and 3.12 s for 1231 nm and were 3.30 s and 3.74 s for 1030 nm of HPBPYFL6 on ITO-glass. The strong NIR electrochromic absorbance of HPBPYFL6 was attributed to intervalence charge transfer by the incorporation of the HPB moiety. This phenomenon was confirmed by chemical oxidation as the oxidant contents increased in the solution state. Furthermore, the electrochromic mechanism was interpreted by DFT calculation and the simulated NIR electrochromic spectra of model compound HPBPYFL are in good agreement with the experimental data.

  4. Synthesis, spectroscopic characterization and antimicrobial activity of binuclear metal complexes of a new asymmetrical Schiff base ligand: DNA binding affinity of copper(II) complexes

    Science.gov (United States)

    Shebl, Magdy

    2014-01-01

    The 1:1 condensation of o-acetoacetylphenol and 1,2-diaminopropane under condition of high dilution gives the mono-condensed Schiff base, (E)-3-(1-aminopropan-2-ylimino)-1-(2-hydroxyphenyl)butan-1-one. The mono-condensed Schiff base has been used for further condensation with isatin to obtain the new asymmetrical dicompartmental Schiff base ligand, (E)-3-(2-((E)-4-(2-hydroxyphenyl)-4-oxobutan-2-ylideneamino) propylimino)indolin-2-one (H3L) with a N2O3 donor set. Reactions of the ligand with metal salts give a series of new binuclear complexes. The ligand and its metal complexes were characterized by elemental analyses, IR, 1H and 13C NMR, electronic, ESR and mass spectra, conductivity and magnetic susceptibility measurements as well as thermal analyses. The analytical and spectroscopic tools showed that the complexes can be formulated as: [(HL)(VO)2(SO4)(H2O)]·4H2O, [(HL)Fe2Cl4(H2O)3]·EtOH, [(HL)Fe2(ox)Cl2(H2O)3]·2H2O, [(L)M2(OAc)(H2O)m]·nH2O; M = Co, Ni or Cu, m = 4, 0 and n = 2, 3, [(HL)Cu2Cl]Cl·6H2O and [(L)(UO2)2(OAc)(H2O)3]·6H2O. The metal complexes exhibited octahedral geometrical arrangements except copper complexes that exhibited tetrahedral geometries and uranyl complex in which the metal ion is octa-coordinated. The Schiff base and its metal complexes were evaluated for antimicrobial activity against Gram positive bacteria (Staphylococcus aureus), Gram negative bacteria (Escherichia coli) and fungi (Candida albicans and Aspergillus flavus). The ligand and some of its complexes were found to be biologically active. The DNA-binding properties of the copper complexes (6 and 7) have been investigated by electronic absorption, fluorescence and viscosity measurements. The results obtained indicate that these complexes bind to DNA via an intercalation binding mode with an intrinsic binding constant, Kb of 1.34 × 104 and 2.5 × 104 M-1, respectively.

  5. Generic approach for synthesizing asymmetric nanoparticles and nanoassemblies

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Yugang; Hu, Yongxing

    2015-05-26

    A generic route for synthesis of asymmetric nanostructures. This approach utilizes submicron magnetic particles (Fe.sub.3O.sub.4--SiO.sub.2) as recyclable solid substrates for the assembly of asymmetric nanostructures and purification of the final product. Importantly, an additional SiO.sub.2 layer is employed as a mediation layer to allow for selective modification of target nanoparticles. The partially patched nanoparticles are used as building blocks for different kinds of complex asymmetric nanostructures that cannot be fabricated by conventional approaches. The potential applications such as ultra-sensitive substrates for surface enhanced Raman scattering (SERS) have been included.

  6. Asymmetric Dimethyl Arginine in Hypothyroid Patients

    International Nuclear Information System (INIS)

    Thyroid diseases may lead to endothelial dysfunction, however, the mechanism underlying the endothelial dysfunction in thyroid disease is still not clear. Asymmetric dimethyl arginine (ADMA), a novel inhibitor of endothelial nitric oxide synthetase (eNOS), was reported to inhibit nitric oxide (NO) synthesis from L-arginine. The present study was carried out to investigate ADMA levels together with effects of dislipidemia in sub-clinical and overt hypothyroid females. There were significant increase in the levels of total cholesterol, low density lipoprotein-cholesterol (LDL-c), high density lipoprotein-cholesterol (HDL-c), thyroid stimulating hormone (TSH) and ADMA in hypothyroid females as compared to controls while the levels of NO and free T4 were significantly decreased than controls. Sub-clinical hypothyroid females had significant high TSH, LDL-c and non-significantly high ADMA levels and total cholesterol as compared to controls while they had significant decrease in NO, HDL-c and non-significant decrease in free T4 as compared to controls. There were significant negative correlations between NO and both ADMA (r2 = 0.84) and free T4 (r2 = 0.95) in overt hypothyroid group while significant positive correlation (r2 = 0.85) was detected between TSH and HDL-c in the same group. These results are highly suggestive that the decrease of nitric oxide secondary to accumulation of ADMA represent an important pathogenic factor together with dyslipidemia in endothelial dysfunction and increased cardiovascular risk especially in hypothyroid females

  7. Advances in total synthesis: A new approach to the synthesis of pteridic acids A and B [Avanços em síntese total: Uma nova abordagem para a síntese dos ácidos pterídicos A e B

    Directory of Open Access Journals (Sweden)

    David Rodrigues da Rocha

    2009-08-01

    Full Text Available This communication overview the total synthesis of pteridic acids A and B recently published by L. C. Dias and A. G. Salles Jr.in The Journal of Organic Chemistry which was achieved by a new synthetic route. These natural products are among the mostcomplex molecules already synthesized in Brazil.

  8. Asymmetric synthesis, structure, and reactivity of unexpectedly stable spiroepoxy-beta-lactones including facile conversion to tetronic acids: application to (+)-maculalactone A.

    Science.gov (United States)

    Duffy, Richard J; Morris, Kay A; Vallakati, Ravikrishna; Zhang, Wei; Romo, Daniel

    2009-07-01

    A novel class of small spirocyclic heterocycles, spiroepoxy-beta-lactones (1,4-dioxaspiro[2.3]-hexan-5-ones), is described that exhibit a number of interesting reactivity patterns. These spiroheterocycles, including an optically active series, are readily synthesized by epoxidation of ketene dimers (4-alkylidene-2-oxetanones) available from homo- or heteroketene dimerization. An analysis of bond lengths in these systems by X-ray crystallography and comparison to data for known spirocycles and those determined computationally suggest that anomeric effects in these systems may be more pronounced due to their rigidity and may contribute to their surprising stability. The synthetic utility of spiroepoxy-beta-lactones was explored, and one facile rearrangement identified under several conditions provides a three-step route from acid chlorides to optically active tetronic acids, ubiquitous heterocycles in bioactive natural products. The addition of various nucleophiles to these spirocycles leads primarily to addition at C5 and C2. The utility of an optically active spiroepoxy-beta-lactone was demonstrated in the concise, enantioselective synthesis of the antifouling agent, (+)-maculalactone A, which proceeds in five steps from hydrocinnamoyl chloride by way of a tetronic acid intermediate. PMID:19453152

  9. Asymmetric Synthesis, Structure, and Reactivity of Unexpectedly Stable Spiroepoxy-β-Lactones Including Facile Conversion to Tetronic Acids: Application to (+)-Maculalactone A

    Science.gov (United States)

    Duffy, Richard J.; Morris, Kay A.; Vallakati, Ravikrishna; Zhang, Wei; Romo, Daniel

    2009-01-01

    A novel class of small spirocyclic heterocycles, spiroepoxy-β-lactones (1,4-dioxaspiro[2.3]-hexan-5-ones), is described that exhibit a number of interesting reactivity patterns. These spiroheterocycles, including an optically active series, are readily synthesized by epoxidation of ketene dimers (4-alkylidene-2-oxetanones) available from homo- or heteroketene dimerization. An analysis of bond lengths in these systems by X-ray crystallography and comparison to data for known spirocycles and those determined computationally, suggest that anomeric effects in these systems may be more pronounced due to their rigidity and may contribute to their surprising stability. The synthetic utility of spiroepoxy-β-lactones was explored and one facile rearrangement identified under several conditions provides a 3-step route from acid chlorides to optically active tetronic acids, ubiquitous heterocycles in bioactive natural products. The addition of various nucleophiles to these spirocycles leads primarily to addition at C5 and C2. The utility of an optically active spiroepoxy-β-lactone was demonstrated in the concise, enantioselective synthesis of the anti-fouling agent, (+)-maculalactone A, which proceeds in 5 steps from hydrocinnamoyl chloride by way of a tetronic acid intermediate. PMID:19453152

  10. The Effect of Prolonged Fasting on Total Lipid Synthesis and Enzyme Activities in the Liver of the European Eel (Anguilla anguilla)

    DEFF Research Database (Denmark)

    Abraham, S. A.; Hansen, Heinz Johs. Max; Hansen, F.N.

    1984-01-01

    The extent of fatty acid synthesis from [1-14C]acetate in liver slices was reduced 6-fold when eels were fasted for 1-7 wk and 20-fold when fasted for 39 wk, thereafter hepatic lipogenesis seemed to remain constant for up to 95 wk of fasting. After a 1-3 wk fast some hepatic enzyme activities were...... total lipid synthesis and lipogenic enzyme activity in eel liver was 30.degree. C....... reduced (acetyl-CoA carboxylase decreased 2-fold and fatty acid synthetase declined 5-fold); others remained unchanged (G-6-P dehydrogenase, 6-phosphogluconate dehydrogenase, .alpha.-glycerol phosphate dehydrogenase as well as malic enzyme and ATP-citrate lyase). The optimum temperature for measuring both...

  11. Bringing the science of proteins into the realm of organic chemistry: total chemical synthesis of SEP (synthetic erythropoiesis protein).

    Science.gov (United States)

    Kent, Stephen B H

    2013-11-11

    Erythropoietin, commonly known as EPO, is a glycoprotein hormone that stimulates the production of red blood cells. Recombinant EPO has been described as "arguably the most successful drug spawned by the revolution in recombinant DNA technology". Recently, the EPO glycoprotein molecule has re-emerged as a major target of synthetic organic chemistry. In this article I will give an account of an important body of earlier work on the chemical synthesis of a designed EPO analogue that had full biological activity and improved pharmacokinetic properties. The design and synthesis of this "synthetic erythropoiesis protein" was ahead of its time, but has gained new relevance in recent months. Here I will document the story of one of the major accomplishments of synthetic chemistry in a more complete way than is possible in the primary literature, and put the work in its contemporaneous context.

  12. 醇腈酶促不对称合成手性氰醇反应条件的研究%Study on the Reaction Conditions for Asymmetric Synthesis of Optically Active Cyanohydrin Catalyzed by Oxynitrilase

    Institute of Scientific and Technical Information of China (English)

    刘森林; 宗敏华; 涂然; 周番; 娄文勇

    2001-01-01

    利用气相色谱手性分析, 对醇腈酶促不对称合成手性氰醇中的pH值、温度、底物浓度和水含量对酶反应速度和非酶反应速度的影响作了研究. 结果表明, 上述因素对酶反应和非酶反应速度均有显著影响. 在水含量较低的非水相酶反应体系中, pH值在4.0以下或反应温度为0~5 ℃时, 非酶反应受到较大程度的抑制, 而酶反应仍具有相对较快的反应速度. 故可获得高光学纯度的产物.%The effects of pH value, temperature, substrate concentration and water content on the enzymatic and non-enzymatic reactions in the asymmetric synthesis of optically active cyanohydrin catalyzed by (R)-oxynitrilase from bitter almond were studied using GC chiral analysis. The conclusion is in non-aqueous organic solvent system with low water content, when pH value is below 4.0 or reaction temperature is 0~5 ℃, the non-enzymatic reaction is greatly inhibited, but oxynitrilase reaction still has relatively high rate. Therefore, the reaction can achieve high enantiomeric purity of the product.

  13. Diverted Total Synthesis of Promysalin Analogs Demonstrates That an Iron-Binding Motif Is Responsible for Its Narrow-Spectrum Antibacterial Activity.

    Science.gov (United States)

    Steele, Andrew D; Keohane, Colleen E; Knouse, Kyle W; Rossiter, Sean E; Williams, Sierra J; Wuest, William M

    2016-05-11

    Promysalin is a species-specific Pseudomonad metabolite with unique bioactivity. To better understand the mode of action of this natural product, we synthesized 16 analogs utilizing diverted total synthesis (DTS). Our analog studies revealed that the bioactivity of promysalin is sensitive to changes within its hydrogen bond network whereby alteration has drastic biological consequences. The DTS library not only yielded three analogs that retained potency but also provided insights that resulted in the identification of a previously unknown ability of promysalin to bind iron. These findings coupled with previous observations hint at a complex multifaceted role of the natural product within the rhizosphere.

  14. Total synthesis of (+)-discodermolide: an improved endgame exploiting a Still-Gennari-type olefination with a C1-C8 beta-ketophosphonate fragment.

    Science.gov (United States)

    Paterson, Ian; Lyothier, Isabelle

    2004-12-23

    [structure: see text] An improved, third-generation, total synthesis of (+)-discodermolide, a potent microtubule-stabilizing anticancer agent of marine sponge origin, is achieved in 11.1% yield over 21 steps. Key steps include a Still-Gennari HWE olefination, performed using NaH as the base, between C1-C8 beta-ketophosphonate 7 and C9-C24 aldehyde 8, introducing the (8Z)-alkene with 10:1 selectivity, and K-Selectride reduction of the derived enone 16, installing the (7S)-configuration.

  15. Radical Beckmann Rearrangement and Its Application in the Formal Total Synthesis of Antimalarial Natural Product Isocryptolepine via C-H Activation.

    Science.gov (United States)

    Mahajan, Pankaj S; Humne, Vivek T; Tanpure, Subhash D; Mhaske, Santosh B

    2016-07-15

    The Beckmann rearrangement of ketoximes, mediated by ammonium persulfate-dimethyl sulfoxide as a reagent, has been achieved under neutral conditions. Based on the radical trapping and (18)O-labeling experiments, the transformation follows a mechanism involving a radical pathway. The scope and generality of the developed protocol has been demonstrated by 19 examples. The developed protocol and Pd-catalyzed intramolecular double C-H activation were used as key steps in the formal total synthesis of antimalarial natural product isocryptolepine. PMID:27377995

  16. Recent advances in catalytic asymmetric hydrogenation:Renaissance of the monodentate phosphorus ligands

    Institute of Scientific and Technical Information of China (English)

    GUO Hongchao; DING Kuiling; DAI Lixin

    2004-01-01

    The history for the development of chiral phosphorus ligands in catalytic asymmetric hydrogenation is briefly highlighted. This review focuses on the recent advances in the synthesis of the monodentate phosphorus ligands and their applications in catalytic asymmetric hydrogenation. The examples highlighted in this article clearly demonstrated the importance and advantages of monodentate phosphorus ligands, which had been ignored for 30 a and experienced a renaissance at the very beginning of this millennium, particularly in the area of asymmetric hydrogenation.

  17. Improved total synthesis and biological evaluation of potent apratoxin S4 based anticancer agents with differential stability and further enhanced activity.

    Science.gov (United States)

    Chen, Qi-Yin; Liu, Yanxia; Cai, Weijing; Luesch, Hendrik

    2014-04-10

    Apratoxins are cytotoxic natural products originally isolated from marine cyanobacteria that act by preventing cotranslational translocation early in the secretory pathway to downregulate receptor levels and inhibit growth factor secretion, leading to potent antiproliferative activity. Through rational design and total synthesis of an apratoxin A/E hybrid, apratoxin S4 (1a), we have previously improved the antitumor activity and tolerability in vivo. Compound 1a and newly designed analogues apratoxins S7-S9 (1b-d), with various degrees of methylation at C34 (1b,c) or epimeric configuration at C30 (1d), were efficiently synthesized utilizing improved procedures. Optimizations have been applied to the synthesis of key intermediate aldehyde 7 and further include the application of Leighton's silanes and modifications of Kelly's methods to induce thiazoline ring formation in other crucial steps of the apratoxin synthesis. Apratoxin S9 (1d) exhibited increased activity with subnanomolar potency. Apratoxin S8 (1c) lacks the propensity to be deactivated by dehydration and showed efficacy in a human HCT116 xenograft mouse model.

  18. Total Chemical Synthesis of a Heterodimeric Interchain Bis-Lactam-Linked Peptide: Application to an Analogue of Human Insulin-Like Peptide 3

    Science.gov (United States)

    Karas, John; Shabanpoor, Fazel; Hossain, Mohammed Akhter; Wade, John D.; Scanlon, Denis B.

    2013-01-01

    Nonreducible cystine isosteres represent important peptide design elements in that they can maintain a near-native tertiary conformation of the peptide while simultaneously extending the in vitro and in vivo half-life of the biomolecule. Examples of these cystine mimics include dicarba, diselenide, thioether, triazole, and lactam bridges. Each has unique physicochemical properties that impact upon the resulting peptide conformation. Each also requires specific conditions for its formation via chemical peptide synthesis protocols. While the preparation of peptides containing two lactam bonds within a peptide is technically possible and reported by others, to date there has been no report of the chemical synthesis of a heterodimeric peptide linked by two lactam bonds. To examine the feasibility of such an assembly, judicious use of a complementary combination of amine and acid protecting groups together with nonfragment-based, total stepwise solid phase peptide synthesis led to the successful preparation of an analogue of the model peptide, insulin-like peptide 3 (INSL3), in which both of the interchain disulfide bonds were replaced with a lactam bond. An analogue containing a single disulfide-substituted interchain lactam bond was also prepared. Both INSL3 analogues retained significant cognate RXFP2 receptor binding affinity. PMID:24288548

  19. Total Chemical Synthesis of a Heterodimeric Interchain Bis-Lactam-Linked Peptide: Application to an Analogue of Human Insulin-Like Peptide 3

    Directory of Open Access Journals (Sweden)

    John Karas

    2013-01-01

    Full Text Available Nonreducible cystine isosteres represent important peptide design elements in that they can maintain a near-native tertiary conformation of the peptide while simultaneously extending the in vitro and in vivo half-life of the biomolecule. Examples of these cystine mimics include dicarba, diselenide, thioether, triazole, and lactam bridges. Each has unique physicochemical properties that impact upon the resulting peptide conformation. Each also requires specific conditions for its formation via chemical peptide synthesis protocols. While the preparation of peptides containing two lactam bonds within a peptide is technically possible and reported by others, to date there has been no report of the chemical synthesis of a heterodimeric peptide linked by two lactam bonds. To examine the feasibility of such an assembly, judicious use of a complementary combination of amine and acid protecting groups together with nonfragment-based, total stepwise solid phase peptide synthesis led to the successful preparation of an analogue of the model peptide, insulin-like peptide 3 (INSL3, in which both of the interchain disulfide bonds were replaced with a lactam bond. An analogue containing a single disulfide-substituted interchain lactam bond was also prepared. Both INSL3 analogues retained significant cognate RXFP2 receptor binding affinity.

  20. Renewable resource management under asymmetric information

    DEFF Research Database (Denmark)

    Jensen, Frank; Andersen, Peder; Nielsen, Max

    2013-01-01

    Asymmetric information between fishermen and the regulator is important within fisheries. The regulator may have less information about stock sizes, prices, costs, effort, productivity and catches than fishermen. With asymmetric information, a strong analytical tool is principal-agent analysis....... In this paper, we study asymmetric information about productivity within a principal-agent framework and a tax on fishing effort is considered. It is shown that a second best optimum can be achieved if the effort tax is designed such that low-productivity agents rent is exhausted, while high-productivity agents...... receive an information rent. The information rent is equivalent to the total incentive cost. The incentive costs arise as we want to reveal the agent's type....

  1. Dc SQUIDs with asymmetric shunt resistors

    Energy Technology Data Exchange (ETDEWEB)

    Rudolph, Matthias; Nagel, Joachim; Kemmler, Matthias; Koelle, Dieter; Kleiner, Reinhold [Physikalisches Institut - Experimentalphysik II and Center for Collective Quantum Phenomena in LISAplus, Universitaet Tuebingen (Germany); Meckbach, Johannes Maximilian; Ilin, Konstantin; Siegel, Michael [Institut fuer Mikro- und Nanoelektronische Systeme, Karlsruhe Institute of Technology, Karlsruhe (Germany)

    2013-07-01

    We have investigated asymmetrically shunted Nb/Al-AlO{sub x}/Nb dc SQUIDs. Simulations based on the coupled Langevin equations predict that the optimum energy resolution ε, and thus also the noise performance of such an asymmetric SQUID, can be 3-4 times better than that of its symmetric counterpart. While keeping the total resistance R identical to a comparable symmetric SQUID with R{sup -1} = R{sub 1}{sup -1} + R{sub 2}{sup -1}, we shunted only one of the two Josephson junctions with R = R{sub 1,2}/2. Both types of SQUIDs were characterized with respect to their transport and noise properties at temperature T = 4.2 K, and we compared the experimental results with numerical simulations. Experiments yielded ε ∼ 32 ℎ for an asymmetric SQUID with an inductance L = 22 pH, whereas a comparable symmetric device achieved ε = 110 ℎ.

  2. An efficient synthesis of loline alkaloids

    Science.gov (United States)

    Cakmak, Mesut; Mayer, Peter; Trauner, Dirk

    2011-07-01

    Loline (1) is a small alkaloid that, in spite of its simple-looking structure, has posed surprising challenges to synthetic chemists. It has been known for more than a century and has been the subject of extensive biological investigations, but only two total syntheses have been achieved to date. Here, we report an asymmetric total synthesis of loline that, with less then ten steps, is remarkably short. Our synthesis incorporates a Sharpless epoxidation, a Grubbs olefin metathesis and an unprecedented transannular aminobromination, which converts an eight-membered cyclic carbamate into a bromopyrrolizidine. The synthesis is marked by a high degree of chemo- and stereoselectivity and gives access to several members of the loline alkaloid family. It delivers sufficient material to support a programme aimed at studying the complex interactions between plants, fungi, insects and bacteria brokered by loline alkaloids.

  3. Asymmetrical international attitudes

    NARCIS (Netherlands)

    Van Oudenhoven, JP; Askevis-Leherpeux, F; Hannover, B; Jaarsma, R; Dardenne, B

    2002-01-01

    In general, attitudes towards nations have a fair amount of reciprocity: nations either like each other are relatively indifferent to each other or dislike each other Sometimes, however international attitudes are asymmetrical. In this study, we use social identity theory in order to explain asymmet

  4. An asymmetric Kadison's inequality

    CERN Document Server

    Bourin, Jean-Christophe

    2010-01-01

    Some inequalities for positive linear maps on matrix algebras are given, especially asymmetric extensions of Kadison's inequality and several operator versions of Chebyshev's inequality. We also discuss well-known results around the matrix geometric mean and connect it with complex interpolation.

  5. Asymmetric catalysis with helical polymers

    NARCIS (Netherlands)

    Megens, Rik P.; Roelfes, Gerard

    2011-01-01

    Inspired by nature, the use of helical biopolymer catalysts has emerged over the last years as a new approach to asymmetric catalysis. In this Concept article the various approaches and designs and their application in asymmetric catalysis will be discussed.

  6. DIFLUORPHOS and SYNPHOS in asymmetric catalysis: Synthetic applications

    Indian Academy of Sciences (India)

    Sebastien Prevost; Tahar Ayad; Jean-Pierre Genet; Phannarath Phansavath; Virginie Ratovelomanana-Vidal

    2014-03-01

    Enantiomerically pure diphosphines play an important role in various homogeneous metalcatalyzed asymmetric reactions. Over the last few years, our group has been involved in the design and synthesis of atropisomeric ligands named SYNPHOS and DIFLUORPHOS with complementary stereoelectronic properties. This paper shows the high catalytic performances of DIFLUORPHOS, SYNPHOS and SYNPHOS analogues for some C-H and C-C bond forming processes as well as for the synthesis of biorelevant targets.

  7. Total Synthesis and Biological Activity of Marine Alkaloid Eudistomins Y1–Y7 and Their Analogues

    Directory of Open Access Journals (Sweden)

    Tao Jiang

    2013-04-01

    Full Text Available Eudistomin Y class compounds are a series of β-carbolines which was originally isolated from a marine turnicate or ascidian near the South Korea Sea. These compounds contain bromo-substituted groups, which is one of the typical characters of marine natural products. We report herein the chemical synthesis and biological evaluation of seven new β-carboline-based metabolites, Eudistomins Y1–Y7, and their hydroxyl-methylated phenyl derivatives. Using bromo-substituted tryptamines and bromo-substituted phenylglyoxals as the key intermediates, Eudistomins Y1–Y7 and their derivatives were synthesized via the acid-catalyzed Pictet-Spengler reaction and fully characterized by 1H- and 13C-NMR and mass spectroscopy. Biological studies revealed that all of the compounds showed moderate growth inhibitory activity against breast carcinoma cell line MDA-231 with IC50 of 15–63 μM and the inhibitory activities of hydroxyl-methylated phenyl products were higher than that of the corresponding natural products Eudistomins Y1–Y7.

  8. Total synthesis of pinnatoxins A and G and revision of the mode of action of pinnatoxin A.

    Science.gov (United States)

    Araoz, Romulo; Servent, Denis; Molgó, Jordi; Iorga, Bogdan I; Fruchart-Gaillard, Carole; Benoit, Evelyne; Gu, Zhenhua; Stivala, Craig; Zakarian, Armen

    2011-07-13

    Pinnatoxins belong to an emerging class of potent marine toxins of the cyclic imine group. Detailed studies of their biological effects have been impeded by unavailability of the complex natural product from natural sources. This work describes the development of a robust, scalable synthetic sequence relying on a convergent strategy that delivered a sufficient amount of the toxin for detailed biological studies and its commercialization for use by other research groups and regulatory agencies. A central transformation in the synthesis is the highly diastereoselective Ireland-Claisen rearrangement of a complex α,α-disubstituted allylic ester based on a unique mode for stereoselective enolization through a chirality match between the substrate and the lithium amide base. With synthetic pinnatoxin A, a detailed study has been performed that provides conclusive evidence for its mode of action as a potent inhibitor of nicotinic acetylcholine receptors selective for the human neuronal α7 subtype. The comprehensive electrophysiological, biochemical, and computational studies support the view that the spiroimine subunit of pinnatoxins is critical for blocking nicotinic acetylcholine receptor subtypes, as evidenced by analyzing the effect of a synthetic analogue of pinnatoxin A containing an open form of the imine ring. Our studies have paved the way for the production of certified standards to be used for mass-spectrometric determination of these toxins in marine matrices and for the development of tests to detect these toxins in contaminated shellfish. PMID:21644584

  9. Asymmetric information and economics

    Science.gov (United States)

    Frieden, B. Roy; Hawkins, Raymond J.

    2010-01-01

    We present an expression of the economic concept of asymmetric information with which it is possible to derive the dynamical laws of an economy. To illustrate the utility of this approach we show how the assumption of optimal information flow leads to a general class of investment strategies including the well-known Q theory of Tobin. Novel consequences of this formalism include a natural definition of market efficiency and an uncertainty principle relating capital stock and investment flow.

  10. Asymmetric Organocatalytic Cycloadditions

    DEFF Research Database (Denmark)

    Mose, Rasmus

    2016-01-01

    were pioneered by Otto Paul Hermann Diels and Kurt Alder who discovered what later became known as the Diels Alder reaction. The Diels Alder reaction is a [4+2] cycloaddition in which a π4 component reacts with a π2 component via a cyclic transition state to generate a 6 membered ring. This reaction...... reactions constitute the first organocatalytic asymmetric higher order cycloadditions and a rational for the periselectivity and stereoselectivity is provided based on experimental and computational investigations....

  11. Asymmetric Synthesis of Perseal B and Viriolin

    Institute of Scientific and Technical Information of China (English)

    XIA,Ya-Mu; WANG,Xiao-Long; LIANG,Qi-Ren; CAO,Xiao-Ping; PAN,Xin-Fu

    2004-01-01

    @@ Perseal B (1) from the leaves of Persea obovatifolia, and viriolin (2) from the leaves of Virola surinamensis belong to 8-O-4' lignan. They show activity against leishmaniasis, a tropical disease transmitted by mosquitoes.

  12. Total synthesis and biological evaluation of a series of macrocyclic hybrids and analogues of the antimitotic natural products dictyostatin, discodermolide, and taxol.

    Science.gov (United States)

    Paterson, Ian; Naylor, Guy J; Gardner, Nicola M; Guzmán, Esther; Wright, Amy E

    2011-02-01

    The design, synthesis, and biological evaluation of a series of hybrids and analogues of the microtubule-stabilizing anticancer agents dictyostatin, discodermolide, and taxol is described. A 22-membered macrolide scaffold was prepared by adapting earlier synthetic routes directed towards dictyostatin and discodermolide, taking advantage of the distinctive structural and stereochemical similarities between these two polyketide-derived marine natural products. Initial endeavors towards accessing novel discodermolide/dictyostatin hybrids led to the adoption of a late-stage diversification strategy and the construction of a small library of methyl-ether derivatives, along with the first triple hybrids bearing the side-chain of taxol or taxotere attached through an ester linkage. Biological assays of the anti-proliferative activity of these compounds in a series of human cancer cell lines, including the taxol-resistant NCI/ADR-Res cell line, allowed the proposal of various structure-activity relationships. This led to the identification of a potent macrocyclic discodermolide/dictyostatin hybrid 12 and its C9 methoxy derivative 38, accessible by an efficient total synthesis and with a similar biological profile to dictyostatin.

  13. Synthesis, structure and total conductivity of A-site doped LaTiO{sub 3−δ} perovskites

    Energy Technology Data Exchange (ETDEWEB)

    Bradha, M. [Nanotech Research Facility, PSG Institute of Advanced Studies, Coimbatore 641 004, TN (India); Hussain, S.; Chakravarty, Sujay [UGC-DAE CSR, Kalpakkam Node, Kokilamedu 603 104, TN (India); Amarendra, G. [UGC-DAE CSR, Kalpakkam Node, Kokilamedu 603 104, TN (India); Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102, TN (India); Ashok, Anuradha, E-mail: anu.machina@gmail.com [Nanotech Research Facility, PSG Institute of Advanced Studies, Coimbatore 641 004, TN (India)

    2015-03-25

    Highlights: • A-site divalent alkaline earth metal doped LaTiO{sub 3−δ} perovskites were synthesised by sol–gel method. • Structural studies revealed no change in crystal symmetry but change in cell dimensions after doping. • After doping divalent cations in A-site, an enhancement in total conductivity was observed in LaTiO{sub 3−δ}. • Temperature dependent electrical property was observed in all synthesised perovskites. - Abstract: Oxygen deficient perovskites LaTiO{sub 3−δ} and La{sub 0.8}A{sub 0.2}TiO{sub 3−δ} (A = Ba, Sr, Ca) were synthesized by sol–gel method. The effect of divalent dopants on microstructure is investigated in detail using X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). The oxidation states of La{sup 3+} and Ti{sup 3+} ions have been deduced using X-ray Photoelectron Spectroscopy (XPS). Impedance spectroscopy was used to analyze the total conductivity, an increase in conductivity was observed after doping in the A-site with divalent cations Ba, Ca and Sr. Among the investigated perovskites La{sub 0.8}Ca{sub 0.2}TiO{sub 3−δ} exhibited the maximum conductivity of 1.22 × 10{sup −2} S/cm in air atmosphere at 650 °C.

  14. Development of a third-generation total synthesis of (+)-discodermolide: an expedient Still-Gennari-type fragment coupling utilizing an advanced beta-ketophosphonate.

    Science.gov (United States)

    Paterson, Ian; Lyothier, Isabelle

    2005-07-01

    [structure: see text] A novel total synthesis of the complex polyketide discodermolide, a promising anticancer agent of marine sponge origin, has been completed in 11.1% overall yield over 21 linear steps. This third-generation approach features an unprecedented Still-Gennari-type HWE olefination reaction between advanced C1-C8 beta-ketophosphonate 61 and C9-C24 aldehyde 7, introducing the (8Z)-alkene with 10:1 selectivity. The stereotetrad found in the C1-C8 subunit 61 was established via a highly diastereoselective boron-mediated aldol reaction/in situ reduction between ketone (S)-8 and 3-benzyloxypropanal. The (7S)-configuration was installed by the reduction of enone 73 with K-Selectride.

  15. Autoradiographic studies on mucilage synthesis in Chara vulgaris antheridium with the use of 3H-fucose in total darkness and light

    International Nuclear Information System (INIS)

    Autoradiographic studies with 3H-fucose have shown that this precursor of polysaccharide compounds is incorporated into manubria and antheridial mucilage of Chara vulgaris both in the light and in the darkness. The dynamic of this process is lower in total darkness. The decrease in overall labelling of antheridium (manubria an mucilage) reflects secondary metabolic changes both in proliferative phase and in spermiogenesis. The pulse (2 and 5 min) incubations with the isotope confirm the intensive mucilage translocation which at later developmental stages is more dynamic than at earlier ones. It can explain previously observed decrease in manubria radioactivity at later stages after long (40 min) incubation, because PAS-positive polysaccharide synthesis is simultaneous with their fast translocation to the antheridial space. The present and previous autoradiographic and cytophotometric data taken altogether confirm the assumption about a nutritive role of mucilage filling Chara antheridium during the process of spermatogenesis. (author). 19 refs, 7 figs

  16. Autoradiographic studies on mucilage synthesis in Chara vulgaris antheridium with the use of {sup 3}H-fucose in total darkness and light

    Energy Technology Data Exchange (ETDEWEB)

    Gosek, A. [Lodz Univ. (Poland)

    1996-12-31

    Autoradiographic studies with {sup 3}H-fucose have shown that this precursor of polysaccharide compounds is incorporated into manubria and antheridial mucilage of Chara vulgaris both in the light and in the darkness. The dynamic of this process is lower in total darkness. The decrease in overall labelling of antheridium (manubria an mucilage) reflects secondary metabolic changes both in proliferative phase and in spermiogenesis. The pulse (2 and 5 min) incubations with the isotope confirm the intensive mucilage translocation which at later developmental stages is more dynamic than at earlier ones. It can explain previously observed decrease in manubria radioactivity at later stages after long (40 min) incubation, because PAS-positive polysaccharide synthesis is simultaneous with their fast translocation to the antheridial space. The present and previous autoradiographic and cytophotometric data taken altogether confirm the assumption about a nutritive role of mucilage filling Chara antheridium during the process of spermatogenesis. (author). 19 refs, 7 figs.

  17. Total replacement of corn by mesquite pod meal considering nutritional value, performance, feeding behavior, nitrogen balance, and microbial protein synthesis of Holstein-Zebu crossbred dairy steers.

    Science.gov (United States)

    de Oliveira Moraes, Gláucia Sabrine; de Souza, Evaristo Jorge Oliveira; Véras, Antonia Sherlânea Chaves; de Paula Almeida, Marina; da Cunha, Márcio Vieira; Torres, Thaysa Rodrigues; da Silva, Camila Sousa; Pereira, Gerfesson Felipe Cavalcanti

    2016-10-01

    The objective of the present study to assess the effects of mesquite pod addition replacing corn (0, 250, 500, 750, and 1000 g/kg in the dry matter basis) on nutrient intake, animal performance, feeding behavior, nutrient digestibility, nitrogen balance, and microbial protein synthesis. Twenty-five Holstein-Zebu crossbred dairy steers at 219 ± 22 kg initial body weight and 18 months of age were used. The experiment lasted 84 days, divided into three periods of 28 days. A completely randomized design was used, and data were submitted to analysis using PROC GLM for analysis of variance and PROC REG for regression analysis using the software Statistical Analysis Systems version 9.1. Experimental diets were composed of Tifton 85 hay, soybean meal, ground corn, mesquite pod meal, and mineral salt. Samples of food offered were collected during the last 3 days of each period, and the leftovers were collected daily, with samples bulked per week. At the end of each 28-day period, the remaining animals were weighed to determine total weight gain and average daily gain. The assessment of behavioral patterns was performed through instantaneous scans in 5-min intervals for three consecutive 12-h days. A single urine sample from each animal was collected on the last day of each collection period at about 4 h after the first feeding. The replacement of corn by mesquite pod meal did not significantly influence treatments regarding nutrients intake, animal performance, and feeding behavior. Retained and consumed nitrogen ratio did not statistically differ between replacement levels. Likewise, there were no statistical differences regarding microbial protein synthesis and efficiency between replacement levels. Mesquite pod meal can be used in Holstein-Zebu crossbred dairy steers' diet with total corn replacement. PMID:27387896

  18. Developing a Practical Chiral Toolbox for Asymmetric Catalytic Reactions

    Institute of Scientific and Technical Information of China (English)

    ZHANG; XuMu

    2001-01-01

    Chiral Quest's Toolbox Approach: During the last several decades, chemists have made major progress in discovering man-made catalysts to perform challenging asymmetric transformations. However, there is no universal chiral ligand or catalyst for solving problems in enantioselective transformations. The focus of Chiral Quest's research is to develop a useful chiral toolbox for strategically important asymmetric catalytic reactions by inventing a diverse set of novel chiral ligands and combining them with transition metals as effective enantioselective catalysts. The toolbox approach addresses significant problems in organic stereochemistry and has resulted in practical methods for the synthesis of chiral pharmaceuticals and agrochemicals  ……

  19. Developing a Practical Chiral Toolbox for Asymmetric Catalytic Reactions

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ Chiral Quest's Toolbox Approach: During the last several decades, chemists have made major progress in discovering man-made catalysts to perform challenging asymmetric transformations. However, there is no universal chiral ligand or catalyst for solving problems in enantioselective transformations. The focus of Chiral Quest's research is to develop a useful chiral toolbox for strategically important asymmetric catalytic reactions by inventing a diverse set of novel chiral ligands and combining them with transition metals as effective enantioselective catalysts. The toolbox approach addresses significant problems in organic stereochemistry and has resulted in practical methods for the synthesis of chiral pharmaceuticals and agrochemicals

  20. Large deviation function of the partially asymmetric exclusion process.

    Science.gov (United States)

    Lee, D S; Kim, D

    1999-06-01

    The large deviation function obtained recently by Derrida and Lebowitz [Phys. Rev. Lett. 80, 209 (1998)] for the totally asymmetric exclusion process is generalized to the partially asymmetric case in the scaling limit. The asymmetry parameter rescales the scaling variable in a simple way. The finite-size corrections to the universal scaling function and the universal cumulant ratio are also obtained to the leading order. PMID:11969632

  1. Asymmetric quantum cloning machines

    International Nuclear Information System (INIS)

    A family of asymmetric cloning machines for quantum bits and N-dimensional quantum states is introduced. These machines produce two approximate copies of a single quantum state that emerge from two distinct channels. In particular, an asymmetric Pauli cloning machine is defined that makes two imperfect copies of a quantum bit, while the overall input-to-output operation for each copy is a Pauli channel. A no-cloning inequality is derived, characterizing the impossibility of copying imposed by quantum mechanics. If p and p' are the probabilities of the depolarizing channels associated with the two outputs, the domain in (√p,√p')-space located inside a particular ellipse representing close-to-perfect cloning is forbidden. This ellipse tends to a circle when copying an N-dimensional state with N→∞, which has a simple semi-classical interpretation. The symmetric Pauli cloning machines are then used to provide an upper bound on the quantum capacity of the Pauli channel of probabilities px, py and pz. The capacity is proven to be vanishing if (√px, √py, √pz) lies outside an ellipsoid whose pole coincides with the depolarizing channel that underlies the universal cloning machine. Finally, the tradeoff between the quality of the two copies is shown to result from a complementarity akin to Heisenberg uncertainty principle. (author)

  2. Multiple Traveling Salesmen in Asymmetric Metrics

    CERN Document Server

    Friggstad, Zachary

    2011-01-01

    We consider some generalizations of the Asymmetric Traveling Salesman Path problem. Suppose we have an asymmetric metric G = (V,A) with two distinguished nodes s,t. We are also given a positive integer k. The goal is to find k paths of minimum total cost from s to t whose union spans all nodes. We call this the k-Person Asymmetric Traveling Salesmen Path problem (k-ATSPP). Our main result for k-ATSPP is a bicriteria approximation that, for some parameter b >= 1 we may choose, finds between k and k + k/b paths of total length O(b log |V|) times the optimum value of an LP relaxation based on the Held-Karp relaxation for the Traveling Salesman problem. On one extreme this is an O(log |V|)-approximation that uses up to 2k paths and on the other it is an O(k log |V|)-approximation that uses exactly k paths. Next, we consider the case where we have k pairs of nodes (s_1,t_1), ..., (s_k,t_k). The goal is to find an s_i-t_i path for every pair such that each node of G lies on at least one of these paths. Simple appro...

  3. Alternative Asymmetric Stochastic Volatility Models

    NARCIS (Netherlands)

    M. Asai (Manabu); M.J. McAleer (Michael)

    2010-01-01

    textabstractThe stochastic volatility model usually incorporates asymmetric effects by introducing the negative correlation between the innovations in returns and volatility. In this paper, we propose a new asymmetric stochastic volatility model, based on the leverage and size effects. The model is

  4. Engineered Asymmetric Synthetic Vesicles

    Science.gov (United States)

    Lu, Li; Chiarot, Paul

    2013-11-01

    Synthetic vesicles are small, fluid-filled spheres that are enclosed by a bilayer of lipid molecules. They can be used as models for investigating membrane biology and as delivery vehicles for pharmaceuticals. In practice, it is difficult to simultaneously control membrane asymmetry, unilamellarity, vesicle size, vesicle-to-vesicle uniformity, and luminal content. Membrane asymmetry, where each leaflet of the bilayer is composed of different lipids, is of particular importance as it is a feature of most natural membranes. In this study, we leverage microfluidic technology to build asymmetric vesicles at high-throughput. We use the precise flow control offered by microfluidic devices to make highly uniform emulsions, with controlled internal content, that serve as templates to build the synthetic vesicles. Flow focusing, dielectrophoretic steering, and interfacial lipid self-assembly are critical procedures performed on-chip to produce the vesicles. Fluorescent and confocal microscopy are used to evaluate the vesicle characteristics.

  5. Asymmetric black dyonic holes

    Directory of Open Access Journals (Sweden)

    I. Cabrera-Munguia

    2015-04-01

    Full Text Available A 6-parametric asymptotically flat exact solution, describing a two-body system of asymmetric black dyons, is studied. The system consists of two unequal counterrotating Kerr–Newman black holes, endowed with electric and magnetic charges which are equal but opposite in sign, separated by a massless strut. The Smarr formula is generalized in order to take into account their contribution to the mass. The expressions for the horizon half-length parameters σ1 and σ2, as functions of the Komar parameters and of the coordinate distance, are displayed, and the thermodynamic properties of the two-body system are studied. Furthermore, the seven physical parameters satisfy a simple algebraic relation which can be understood as a dynamical scenario, in which the physical properties of one body are affected by the ones of the other body.

  6. Stereoselective total synthesis of sphingolipids

    Indian Academy of Sciences (India)

    PARAMESH JANGILI; PERLA RAMESH; BISWANATH DAS

    2016-11-01

    A novel sphingosine, 1,2-diacetyl D-erythro-sphinganine having a characteristic almond flavour was isolated from the edible mushroom Grifola gargal. We have synthesized this sphinganine along with the three other sphingolipids, such as 1,2-diacetyl L-threo-sphinganine, D-erythro-sphinganine triacetateand L-threo-sphinganine triacetate using Garner aldehyde as the starting material involving the Grignard reaction and Mitsunobu inversion. The sphingolipids 1,2-diacetyl D-erythro-sphinganine and 1,2-diacetyl L-threo-sphinganine have been synthesized for the first time.

  7. Total synthesis of (-)- and (+)-tedanalactam

    Digital Repository Service at National Institute of Oceanography (India)

    Majik, M.S.; Parameswaran, P.S.; Tilve, S.G.

    are given in Hz. Chiral HPLC analyses was executed using Jasco HPLC model MX-2080-31 instrument. tert-Butyl (3-hydroxypropyl)carbamate (10): The Boc 2 O (5.83 g, 0.026 mol) was added drop wise to a stirred solution of 3-amino-1-propanol 9 (1.744 g, 0... were recorded on a MicroMass ES- QTOF. Chiral HPLC analysis was executed using Jasco HPLC model MX-2080-31 instrument. Melting points were recorded using Thiele apparatus and are uncorrected. S2 2. Copies of 1 H NMR, 13 C NMR and DEPT...

  8. Total Synthesis of Securinega Alkaloids

    Institute of Scientific and Technical Information of China (English)

    T. Honda

    2005-01-01

    @@ 1Introduction Naturally occurring Securinega alkaloids (1-4) (Fig. 1)[1], with their wide range of structural and stereochemical features, continue to provide challenging synthetic targets, since these alkaloids exhibit attractive biological activities. Securinine (1), isolated from Securinega suffruticosa [2], was structurally determined to contain an indolizidine skeleton with an azabicyclo[3.2.1 ]octane system together with an α, β-unsaturated γ-lactone ring. This alkaloid has been clinically used in Russia as a CNS stimulating drug[3], and has been shown to act as a stereospecific antagonist at the GABA binding site of the GABAA-receptor complex[4].Viroallosecurinine (2), a diastereoisomeric alkaloid of securinine, was also isolated from the leaves of Securinega virosa[5] as a cytotoxic alkaloid exhibiting a MIC of 0.48 μg/mL for Ps. aeruginosa and Staph.aureus[6]. This alkaloid is recognized to be bactericidal since the yields of MIC/MBC were less than 1[7].

  9. Total synthesis and evaluation of vinblastine analogues containing systematic deep-seated modifications in the vindoline subunit ring system: core redesign.

    Science.gov (United States)

    Schleicher, Kristin D; Sasaki, Yoshikazu; Tam, Annie; Kato, Daisuke; Duncan, Katharine K; Boger, Dale L

    2013-01-24

    The total synthesis of a systematic series of vinblastine analogues that contain deep-seated structural modifications to the core ring system of the lower vindoline subunit is described. Complementary to the vindoline 6,5 DE ring system, compounds with 5,5, 6,6, and the reversed 5,6 membered DE ring systems were prepared. Both the natural cis and unnatural trans 6,6-membered ring systems proved accessible, with the latter representing a surprisingly effective class for analogue design. Following Fe(III)-promoted coupling with catharanthine and in situ oxidation to provide the corresponding vinblastine analogues, their evaluation provided unanticipated insights into how the structure of the vindoline subunit contributes to activity. Two potent analogues (81 and 44) possessing two different unprecedented modifications to the vindoline subunit core architecture were discovered that matched the potency of the comparison natural products and both lack the 6,7-double bond whose removal in vinblastine leads to a 100-fold drop in activity.

  10. Part 1. Approaches to the total synthesis of the diterpene marrubin. Part II. Ligand assisted nucleophilic additions. Part III. Coal processing in a non-dissolving medium

    Energy Technology Data Exchange (ETDEWEB)

    Lipscombe, J.; Charles, W. II

    1987-01-01

    The total synthesis of the diterpene marrubiin was attempted using methodology previously developed in the Liotta laboratories. Ligand Assisted Nucleophilic Additions (LANA) comprise a new class of synthetic reactions involving the stereoselective addition of some group, usually in an intramolecular conjugate fashion. This group is itself derived from an earlier nucleophilic addition to a carbonyl moiety. Exchange of the original metal of the alkoxide with a second metal (which must be at least divalent) having a transferrable group demands that the stereochemistry of the first addition control the second. The general features of these types of processes are discussed. Initial work with substituted quinones is presented, and some mechanistic rationales are given. A novel method of coal processing at modest temperatures and hydrogen pressures (250-300/sup 0/C, 8.0 MPa) is discussed. Coals reacted with small amounts of tetrahydroquinoline in the presence of fluorocarbons or other non-dissolving media underwent astounding increases in pyridine solubility, a common standard in coal liquefaction studies. Several additives were employed, although only tetrahydroquinoline was found to effectively increase coal solubility. Coals having vastly different individual properties behaved similarly under these conditions. Kinetic and model studies were used in an attempt to clarify the reactions occurring under these novel conditions.

  11. Asymmetric 1,4-bis(ethynylbicyclo[2.2.2]octane rotators via monocarbinol functionalization. Ready access to polyrotors

    Directory of Open Access Journals (Sweden)

    Cyprien Lemouchi

    2015-10-01

    Full Text Available Asymmetric rotators with a 1,4-bis(ethynylbicyclo[2.2.2]octane (BCO core are needed for engineering crystalline arrays of functional molecular rotors. Their synthesis uses carbinol, 2-methyl-3-butyn-2-ol, as a protecting group because of its polar character and its ability to sustain orthogonal functionalization with the further advantage of being readily removed. The synthesis in good yields of unprecedented asymmetric rotors and polyrotors demonstrates the efficiency of this strategy.

  12. Asymmetric Aldol Reaction Catalyzed by Modularly Designed Organocatalysts

    Institute of Scientific and Technical Information of China (English)

    Sinha, Debarshi; Mandal, Tanmay; Gogoi, Sanjib; Goldman, Joshua J.; 赵从贵

    2012-01-01

    The self-assembly of the precatalyst modules, which are amino acids and cinchona alkaloid derivatives, leads to the direct formation of the desired organocatalysts without any synthesis. These modularly designed organocatalysts (MDOs) may be used for catalyzed asymmetric aldol reaction the corresponding aldol products may be obtained in mediocre diastereoselectivities (up to 79 : 21 dr). Depending on structure of the aldehyde substrates, to excellent ee values (up to 92% ee) with moderate

  13. Condensation and transport in the totally asymmetric inclusion process (TASIP)

    Science.gov (United States)

    Knebel, Johannes; Weber, Markus F.; Krueger, Torben; Frey, Erwin

    Transport phenomena are often modeled by the hopping of particles on regular lattices or networks. Such models describe, e.g., the exclusive movement of molecular motors along microtubules: no two motors may occupy the same site. In our work, we study inclusion processes that are the bosonic analogues of the fermionic exclusion processes. In inclusion processes, many particles may occupy a single site and hopping rates depend linearly on the occupation of departure and arrival sites. Particles thus attract other particles to their own site. Condensation occurs when particles collectively cluster in one or multiple sites, whereas other sites become depleted.We showed that inclusion processes describe both the selection of strategies in evolutionary zero-sum games and the condensation of non-interacting bosons into multiple quantum states in driven-dissipative systems. The condensation is captured by the antisymmetric Lotka-Volterra equation (ALVE), which constitutes a nonlinearly coupled dynamical system. We derived an algebraic method to analyze the ALVE and to determine the condensates. Our approach allows for the design of networks that result in condensates with oscillating occupations, and yields insight into the interplay between network topology and transport properties. Deutsche Forschungsgemeinschaft (SFB-TR12), German Excellence Initiative (Nanosystems Initiative Munich), Center for NanoScience Munich.

  14. Asymmetric Gepner Models (Revisited)

    CERN Document Server

    Gato-Rivera, B

    2010-01-01

    We reconsider a class of heterotic string theories studied in 1989, based on tensor products of N=2 minimal models with asymmetric simple current invariants. We extend this analysis from (2,2) and (1,2) spectra to (0,2) spectra with SO(10) broken to the Standard Model. In the latter case the spectrum must contain fractionally charged particles. We find that in nearly all cases at least some of them are massless. However, we identify a large subclass where the fractional charges are at worst half-integer, and often vector-like. The number of families is very often reduced in comparison to the 1989 results, but there are no new tensor combinations yielding three families. All tensor combinations turn out to fall into two classes: those where the number of families is always divisible by three, and those where it is never divisible by three. We find an empirical rule to determine the class, which appears to extend beyond minimal N=2 tensor products. We observe that distributions of physical quantities such as th...

  15. Synthesis of 3-Substituted BINOL derivatives and application in asymmetric epoxidation reaction%手性3-取代联二萘酚衍生物的合成及在不对称环氧化中的应用

    Institute of Scientific and Technical Information of China (English)

    尤强; 王琳; 宋华; 何玉玲; 牟瑶; 王钦; 王力

    2013-01-01

    目的:研究α,β不饱和酮的不对称环氧化反应。方法:利用手性的3-取代联二萘酚和Fe3+、La3+、Al3+的配和物诱导不对称环氧化反应。结果:成功合成了三个3取代联二萘酚衍生物,并将其运用于不对称环氧化反应。手性La3+配合物催化的环氧化反应,取得88%的产率以及46%对映异构体过量;手性Fe3+和Al3+配合物体系,环氧化产率较高,产物为消旋体。结论:手性的3-羟甲基联二萘酚镧配合物能够催化α,β不饱和酮的不对称环氧化反应并获得较高产率和中等的对映选择性。对该不对称环氧化反应的研究,为合成光活性环氧化物类药物中间体提供了新方法。%Objective: To study the asymmetric epoxidation of α,β-unsaturated ketone with BINOL derivative as catalyst. Method: The chiral 3-substitued-BINOL derivative ligands were first synthesized ,and then coordinated with Fe3+, La3+or Al3+to catalyze the asymmetric epoxidation of chalcone. Results: The 3-substituted BINOL derivatives (4~5) were successfully synthesized and applied in the asymmetric epoxidation of chalcone. The optical active epoxide was obtained in high yield (88%) and moderate ee value (46%) with 3-hydroxyl-methylnaphthol/La3+ as catalyst,while poor enantioselectivity was observed when the 3-hydroxylmethylnaphthol/Fe3+or 3-hydroxylmethylnaphthol/Al3+complex was used. Conclusion: The chiral 3-hydroxylmethylnaphthol/La3+complex is able to catalyze the asymmetric epoxidation of chalcone in high yield and moderate enantioselectivity , which pvovides a new approach to the construction of optical epoxide intermediate in the synthesis of material and medicine.

  16. Asymmetric Hydrogenation of α-Hydroxy Ketones: A Reaction Sensitive toward Electronic Effect of Substrates

    Institute of Scientific and Technical Information of China (English)

    XU Hui; MENG Qing-Hua; ZHANG Zhao-Guo

    2008-01-01

    An efficient asymmetric hydrogenation of a-hydroxy ketones was reported with the catalyst prepared from [RuCl2(benzene)]2 and SunPhos,chiral terminal 1,2-diols were obtained in up to 99% ee.This Ru-catalyzed asymmetric hydrogenation reaction of a-hydroxy ketones represents a new route for the synthesis of chiral terminal 1,2-diols.

  17. Magnetically Modified Asymmetric Supercapacitors Project

    Data.gov (United States)

    National Aeronautics and Space Administration — This Small Business Innovation Research Phase I project is for the development of an asymmetric supercapacitor that will have improved energy density and cycle...

  18. Multicatalyst system in asymmetric catalysis

    CERN Document Server

    Zhou, Jian

    2014-01-01

    This book introduces multi-catalyst systems by describing their mechanism and advantages in asymmetric catalysis.  Helps organic chemists perform more efficient catalysis with step-by-step methods  Overviews new concepts and progress for greener and economic catalytic reactions  Covers topics of interest in asymmetric catalysis including bifunctional catalysis, cooperative catalysis, multimetallic catalysis, and novel tandem reactions   Has applications for pharmaceuticals, agrochemicals, materials, and flavour and fragrance

  19. On Asymmetric Quantum MDS Codes

    CERN Document Server

    Ezerman, Martianus Frederic; Ling, San

    2010-01-01

    Assuming the validity of the MDS Conjecture, the weight distribution of all MDS codes is known. Using a recently-established characterization of asymmetric quantum error-correcting codes, linear MDS codes can be used to construct asymmetric quantum MDS codes with $d_{z} \\geq d_{x}\\geq 2$ for all possible values of length $n$ for which linear MDS codes over $\\F_{q}$ are known to exist.

  20. Mobile Termination with Asymmetric Networks

    OpenAIRE

    Dewenter, Ralf; Haucap, Justus

    2003-01-01

    This paper examines mobile termination fees and their regulation when networks are asymmetric in size. It is demonstrated that with consumer ignorance about the exact termination rates (a) a mobile network?s termination rate is the higher the smaller the network?s size (as measured through its subscriber base) and (b) asymmetric regulation of only the larger operators in a market will, ce-teris paribus, induce the smaller operators to increase their termination rates. The results are supporte...