12 hirsuteneの分離と構造決定

抄録

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.