Biosynthetic conversion of thebaine to codeinone. Mechanism of ketone formation from enol ether in vivo

International Nuclear Information System (INIS)

Horn, J.S.; Paul, A.G.; Rapoport, H.

1978-01-01

Biosynthesis of the morphinan alkaloids proceeds by conversion of the enol ether or thebaine to the keto group of neopinone and thence to codeinone. To determine the mechanism of this transformation, [G- 14 C,6- 18 O]thebaine was fed to Papaver somniferum and the codeine and morphine were isolated. Comparison of the 18 O/ 14 C ratios in the codeine and morphine isolated with that of the thebaine fed showed that approximately 34% of the 18 O had been retained. Parallel feedings with [G- 14 C,6- 18 O]-codeinone demonstrated that the loss was due to nonenzymic exchange. Thus, the mechanism of enol ether cleavage in thebaine is established as cleavage of the 6-O-methyl group with retention of the 6-oxygen in the codeinone

A Tale of Three Cell Types: Alkaloid Biosynthesis Is Localized to Sieve Elements in Opium Poppy

Science.gov (United States)

Bird, David A.; Franceschi, Vincent R.; Facchini, Peter J.

2003-01-01

Opium poppy produces a diverse array of pharmaceutical alkaloids, including the narcotic analgesics morphine and codeine. The benzylisoquinoline alkaloids of opium poppy accumulate in the cytoplasm, or latex, of specialized laticifers that accompany vascular tissues throughout the plant. However, immunofluorescence labeling using affinity-purified antibodies showed that three key enzymes, (S)-N-methylcoclaurine 3′-hydroxylase (CYP80B1), berberine bridge enzyme (BBE), and codeinone reductase (COR), involved in the biosynthesis of morphine and the related antimicrobial alkaloid sanguinarine, are restricted to the parietal region of sieve elements adjacent or proximal to laticifers. The localization of laticifers was demonstrated using antibodies specific to the major latex protein (MLP), which is characteristic of the cell type. In situ hybridization showed that CYP80B1, BBE, and COR gene transcripts were found in the companion cell paired with each sieve element, whereas MLP transcripts were restricted to laticifers. The biosynthesis and accumulation of alkaloids in opium poppy involves cell types not implicated previously in plant secondary metabolism and dramatically extends the function of sieve elements beyond the transport of solutes and information macromolecules in plants. PMID:14508000