β-Siloxy unsaturated nitriles:: stereodivergent cyclizations to cis- and trans-decalins

被引：12

作者：

Fleming, FF ^{[1
]}

Shook, BC ^{[1
]}

Jiang, T ^{[1
]}

Steward, OW ^{[1
]}

机构：

[1] Duquesne Univ, Dept Chem & Biochem, Pittsburgh, PA 15282 USA

来源：

TETRAHEDRON | 2003年 / 59卷 / 06期

基金：

美国国家卫生研究院;

关键词：

decalin; stereoselectivity; terpenoids; nitrile anions;

D O I：

10.1016/S0040-4020(02)01615-0

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Nitrile and enolate anions exhibit divergent intramolecular cyclization stereoselectivities. Enolates cyclize to cis-decalones, whereas nitrile anions are predisposed to pyramidalize, cyclizing instead through a less-congested conformation to trans-decalins. Conjugation of nitrile anions with adjacent sp(2) centers prevents pyramidalization, and redirects cyclization through a planar-delocalized anion to cis-decalins. Collectively these cyclizations allow conversion of a single beta-siloxynitrile to either cis- or trans-decalins that are ideally suited for elaboration into terpenoid natural products. (C) 2003 Elsevier Science Ltd. All rights reserved.

引用

页码：737 / 745

页数：9

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