著者

Kozo MACHIYA Itsuo ICHIMOTO Kennosuke TONARI Mitsunori KIRIHATA Hiroo UEDA

出版者

Japan Society for Bioscience, Biotechnology, and Agrochemistry

雑誌

Agricultural and Biological Chemistry (ISSN:00021369)

巻号頁・発行日

vol.49, no.6, pp.1767-1773, 1985 (Released:2006-03-27)

参考文献数

12

被引用文献数

3

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A convenient synthetic method for (±)-malyngolide (1), an antibiotic from the marine blue-green alga Lyngbya majuscula GOMONT, is described. The compound (±)-1 was synthesized from 2-methylglutaric anhydride (starting material) in four steps, involving the TBHP-based osmiumcatalyzed procedure for vicinal dihydroxylation of the methylene unit in unsaturated carboxylic acid as the key step. The optical resolution of (±)-1 was accomplished by HPLC, in which diastereomeric (+)-2-(4-chlorophenyl)isovaleric acid [(+)-CPIA] esters of (±)-1 derived from (+)-CPIA-C1 could be easily separated, and subsequent hydrolysis of each ester gave the enantiomerically pure (-)-1 and (+)-1, respectively. A synthetic method for α-methylene malyngolide, which is to be expected for biological activity, is also described.

著者

Itsuo ICHIMOTO Kozo MACHIYA Mitsunori KIRIHATA Hiroo UEDA

出版者

Japan Society for Bioscience, Biotechnology, and Agrochemistry

雑誌

Agricultural and Biological Chemistry (ISSN:00021369)

巻号頁・発行日

vol.54, no.3, pp.657-662, 1990 (Released:2006-04-05)

参考文献数

15

被引用文献数

10

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A convenient synthetic method for the marine antibiotic (-)-malyngolide and its Stereoisomers was accomplished from a chiral α-alkoxyketone (4), which was readily available as a chiron. Chiral quaternary carbon synthons (5a) and (5b) as the key intermediates were constructed by the chelation controlled addition of Grignard reagent to 4. The diastereomeric mixture of 5a and 5b was readily transformed into a separable mixture of lactones (7a) and (7b), each of which could be easily separated by silica-gel column chromatography. (-)-Malyngolide and its three steroisomers were obtained in optically pure form without the need for optical resolution.