Studies on retro-[1,4] Brook rearrangement of 3-silyl allyloxysilanes. Observation of the formation of unusual 3,3-bissilyl enols

被引：15

作者：

Gan, Zubao

Wu, Ya

Gao, Lu

Sun, Xianwei

Lei, Jian

Song, Zhenlei ^{[1
]}

Li, Linjie

机构：

[1] Sichuan Univ, Educ Minist, Key Lab Drug Targeting, Chengdu 610041, Peoples R China

来源：

TETRAHEDRON | 2012年 / 68卷 / 34期

基金：

中国国家自然科学基金;

关键词：

Bissilyl compound; Retro-[1,4] Brook rearrangement; 3-Silyl allyloxysilane; Enol; SILICON-CONTAINING COMPOUNDS; NAZAROV CYCLIZATION; ORGANIC-SYNTHESIS; TERMINATED CYCLIZATION; REACTIVITY; CARBANIONS; CARBONYL; DERIVATIVES; MIGRATION; ANIONS;

D O I：

10.1016/j.tet.2012.06.005

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Detailed investigations of the retro-[1,4] Brook rearrangement of 3-silyl allyloxysilanes are described. Based on control experiments and NMR studies, rationalizations are proposed for the formation of 3,3-bissilyl enols, unusual compounds that are stable to acidic hydrolysis but that can be transformed into the corresponding aldehydes under basic hydrolysis conditions. These studies further show that the 3,3-bissilyl enolates can be O-alkylated by alkyl halides with complete chemoselectivity. This reaction provides a practical entry to various 3,3-bissilyl aldehydes and enol derivatives. As a demonstration of the synthetic utility of this approach, 3,3-bissilyl aldehyde was converted into bissilyl divinyl ketone, which can undergo an SiO2-promoted Nazarov reaction to give cyclic beta-silyl enone smoothly. (C) 2012 Elsevier Ltd. All rights reserved.

引用

页码：6928 / 6934

页数：7

共 41 条

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