通过 3-硅基烯丙基氧硅烷的反-[1,4] Brook 重排高效合成 3,3-双硅基羰基和烯醇衍生物。

Efficient approach to 3,3-bissilyl carbonyl and enol derivatives via retro-[1,4] brook rearrangement of 3-silyl allyloxysilanes.

机构信息

Key Laboratory of Drug-Targeting of Education Ministry and Department of Medicinal Chemistry, West China School of Pharmacy, and State Key Laboratory of Biotherapy, Sichuan University, Chengdu, 610041, PR China.

出版信息

Org Lett. 2010 Nov 19;12(22):5298-301. doi: 10.1021/ol102352w. Epub 2010 Oct 28.

DOI:10.1021/ol102352w

PMID:21028787

Abstract

A facile and highly stereoselective retro-[1,4] Brook rearrangement of 3-silyl allyloxysilanes has been discovered. While basic hydrolysis of the formed (Z)-3,3-bissilyl lithium enolates provides 3,3-bissilyl carbonyl compounds efficiently, trapping the species with various electrophiles including alkyl halides leads to the exclusive O-substituted (Z)-3,3-bissilyl enol derivatives that can undergo a Sakurai reaction with aldehyde to produce the synthetically useful 1,2-diol diastereoselectively.

摘要

我们发现了一种简便且高度对映选择性的[1,4] Brook 重排反应，可用于 3-硅基烯丙基氧基硅烷。通过碱性水解形成的（Z）-3,3-双硅基锂烯醇盐可以有效地提供 3,3-双硅基羰基化合物，而用各种亲电试剂（包括烷基卤化物）捕获该物种，则可以得到（Z）-3,3-双硅基烯醇衍生物的 O-取代物，这些衍生物可以与醛进行 Sakurai 反应，以立体选择性地生成合成上有用的 1,2-二醇。