12 hirsuteneの分離と構造決定

概要

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The crude metabolite obtained from the cultured micellium of Coriolus consor a mushroom which produces coriolin and the related compounds was found to contain a hydrocarbon, hirsutene which has been thought to be a biosynthetic intermediate of coriolin, hirsutic acid and complicatic acid etc. The hydrocarbon fraction was purified by preparative tic(silica gel/AgNO_3/benzene) to afford pure hirsutene4, C_<15>H_<24>(M^+, 204), which was converted to the norketone 6, C_<14>H_<22>O (M+, 206)(ir; 1740 cm^<-1>) by oxidative cleavage. In order to confirm the structure , and to prepare the labelled substrate for biosynthetic study, total synthesis of hirsutene was attempted. Cope rearrangement of the diene 9 obtained from the known ketone 8 afforded the diene 10 in quantitative yield. Oxidative shortening of the side chain followed by treatment with oxalyl chloride gave the acid chloride , which was cyclized to the tricyclic ketone 13 (SnCl_4/CS_2). Reductive removal of chlorin followed by Wittig methylenation yielded hirsutene which was shown to be identical with natural hydrocarbon. Preparation and feeding experiment of labelled hydrocarbon are under investigation.
天然有機化合物討論会の論文
1975-10-01