72985-00-3Relevant articles and documents
Microbial Stereodifferentiating Reduction of (+/-)4-Methyl- and (+/-)-6-Methyl-1-oxometacyclophanes and Revision of the Absolute Configuration of 4-Substituted Metacyclophanes
Nakazaki, Masao,Hirose, Yoshiki,Shimizu, Toru,Suzuki, Takaaki,Ishii, Akira,Makimura, Masaru
, p. 1428 - 1435 (2007/10/02)
Partial oxidative hydrolysis of 4-bromo-1,1,10,10-bis(trimethylenedithio)metacyclophane (7) yielded the bromo ketones 8 and 9 which were respectively converted into (+/-)-4-methyl- (3) and (+/-)-6-methyl-1-oxometacyclophanes (4).The unambiguous synthesis of (+/-)-3 from 2,5-dimethylbenzoic acid (18) assigned their structures.Incubation of (+/-)-3 with Rhodotorula rubra gave a mixture of (-)-ketone 3, (-) axial alcohol 38, and (-) equatorial alcohol 39.The observed (-) Cotton effect indicated the pS configuration of (-)-3, and transformation of (-)-3 into (+)-4-methylmetacyclophane (5) permitted the assignment of the pR configuration to (+)-5, opposite to Schloegl's proposal.This conclusion was further supported by the parallel sequence of the steps starting from (+/-)-6-methyl ketone.