[1,5]-Brook 重排：一种被忽视但很有价值的硅迁移反应，可用于合成构型确定的乙烯基硅烷。偕二（硅烷）的独特空间和电子效应。

[1,5]-Brook rearrangement: an overlooked but valuable silyl migration to synthesize configurationally defined vinylsilane. The unique steric and electronic effects of geminal bis(silane).

机构信息

Key Laboratory of Drug-Targeting and Drug Delivery System of the Education Ministry, Department of Medicinal Chemistry, West China School of Pharmacy, Sichuan University, Chengdu, 610041, China.

出版信息

Chem Commun (Camb). 2013 Oct 11;49(79):8961-3. doi: 10.1039/c3cc45002c.

DOI:10.1039/c3cc45002c

PMID:23963407

Abstract

An unusual [1,5]-Brook rearrangement of the lithium alkoxide of geminal bis(silyl) homoallylic alcohol is described. The unique steric and electronic effects of geminal bis(silane) were found to be crucial for promoting this long-range silyl migration, as well as for facilitating the subsequent γ/Z-selective addition of silyl allyllithium with carbonyl compounds to synthesize diverse configurationally defined Z-vinylsilanes.

摘要

描述了偕二（硅基）烯丙醇锂的烷氧基锂发生的不寻常的[1,5]-Brook 重排。发现偕二（硅烷）独特的空间和电子效应对于促进这种远程硅迁移以及随后的硅烯丙基锂与羰基化合物的γ/Z-选择性加成以合成各种构型定义的 Z-乙烯基硅烷至关重要。