Enantioselective total synthesis of (-)-strychnine: development of a highly practical catalytic asymmetric carbon-carbon bond formation and domino cyclization

被引：45

作者：

Ohshima, T ^{[1
]}

Xu, YJ ^{[1
]}

Takita, R ^{[1
]}

Shibasaki, M ^{[1
]}

机构：

[1] Univ Tokyo, Grad Sch Pharmaceut Sci, Bunkyo Ku, Tokyo 1130033, Japan

来源：

TETRAHEDRON | 2004年 / 60卷 / 43期

关键词：

enantioselective total synthesis; (-)-strychnine; catalytic asymmetric Michael reaction; Domino cyclization;

D O I：

10.1016/j.tet.2004.06.141

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

An enantioselective total synthesis of (-)-strychnine was accomplished through the use of the highly practical catalytic asymmetric Michael reaction (0.1 mol% of (R)-ALB, greater than kilogram scale, without chromatography, 91% yield and >99% ee), and a domino cyclization that simultaneously constructed the B- and D- rings of strychnine (>77% yield). Newly-developed reaction conditions for thionium ion cyclization, NaBH3CN reduction of the imine moiety in the presence of a Lewis acid to prevent the ring-opening reaction, and chemoselective reduction of the thioether (desulfurization) in the presence of exocyclic olefin were pivotal to complete the synthesis. The described chemistry paves the way for the synthesis of more advanced Strychnos alkaloids. (C) 2004 Elsevier Ltd. All rights reserved.

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页码：9569 / 9588

页数：20

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