A CONCISE, STEREOCONTROLLED THIAZOLIUM YLIDE APPROACH TO KAINIC ACID

被引：69

作者：

MONN, JA

VALLI, MJ

机构：

[1] Central Nervous System Diseases Research, Lilly Research Laboratories, A Division of Eli Lilly Company, Lilly Corporate Center, Indianapolis

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1994年 / 59卷 / 10期

关键词：

D O I：

10.1021/jo00089a022

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Racemic alpha-kainic acid (1) has been prepared from (1SR,2SR,5RS)-ethyl (N-(benzyloxycarbonyl)3-aza-6-oxobicyclo[3.3.0] octane-2-carboxylate (11) in ca. 16% overall yield via a concise six-step synthetic sequence. Compound 11 is prepared pn a large scale in 50% yield via the [3 + 2] cycloaddition of thiazolium ylide 9 and 2-cyclopentenone, which provides the requisite 2,3-trans, 3,4-cis stereochemical array about the trisubstituted pyrrolidine nucleus in 1. Chemoselective addition of the one-to-one adduct of MeLi and TiCl4 to the ketone functionality in 11 followed by dehydration, oxidative ring opening, and nonbasic methylenation of the stereochemically labile C4 acetate moiety with CH2I2-Zn-TiCl4 affords the fully protected penultimate intermediate 17 which is exhaustively hydrolyzed to provide 1. This represents a highly efficient and stereocontrolled preparation of (+/-)-alpha-kainic acid.

引用

页码：2773 / 2778

页数：6

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