著者

森本 俊明 阿知波 一雄 千葉 三男

出版者

天然有機化合物討論会実行委員会

雑誌

天然有機化合物討論会講演要旨集 31 (ISSN:24331856)

巻号頁・発行日

pp.183-189, 1989-09-17 (Released:2017-08-18)

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We found that neutral and cationic rhodium (I) complexes of (S,S)- or (R,R)-MOD-DIOP (1 or 2) showed very high enantio-selectivity in the catalytic asymmetric hydrogenation of α-arylidenesuccinic acid half-esters (3). The optically active α-aryl-methylsuccinic acid half-esters (4) obtained are useful inter-madiates for the synthesis of optically active lignans. Total syntheses of (+)-collinusin (7), (-)-deoxypodophyllotoxin (9), and (+)-neoisostegane (14) were achieved using asymmetric hydrogenation catalyzed by the rhodium(I) complex with (S,S)-MOD-DIOP (2) as a key reaction. Thus, the absolute configurations of natural (+)-collinusin (7) and (+)-neoisostegane (14) were determined to be (R) and (M,6R,7R), respectively. The present asymmetric hydrogenation can provide a practical method for the synthesis of various optically active lignans.