用钡试剂对羰基化合物和亚胺进行选择性炔丙基化反应。

Selective propargylation of carbonyl compounds and imines with barium reagents.

作者信息

Yanagisawa Akira, Suzuki Takahiro, Koide Takanori, Okitsu Shogo, Arai Takayoshi

机构信息

Department of Chemistry, Graduate School of Science, Chiba University, Inage, Chiba, Japan.

出版信息

Chem Asian J. 2008 Oct 6;3(10):1793-800. doi: 10.1002/asia.200800264.

DOI:10.1002/asia.200800264

PMID:18770517

Abstract

A Barbier-type regioselective propargylation of aldehydes and ketones with (3-bromobut-1-ynyl)trimethylsilane has been achieved using reactive barium as a low-valent metal in THF. Especially in the case of ketones, the corresponding homopropargylic alcohols form almost exclusively. In the reaction of alpha,beta-unsaturated carbonyl compounds, only 1,2-adducts have been observed. This method is also applicable to propargylation of imines, and the corresponding homopropargylic amines are obtained regiospecifically in good yields with diastereomeric ratios of up to 87:13.

摘要

在四氢呋喃中，使用活性钡作为低价金属，实现了醛和酮与(3-溴丁-1-炔基)三甲基硅烷的巴比耶型区域选择性炔丙基化反应。特别是对于酮，几乎只生成相应的高炔丙醇。在α,β-不饱和羰基化合物的反应中，仅观察到1,2-加成产物。该方法也适用于亚胺的炔丙基化反应，并且能以高达87:13的非对映体比例区域选择性地获得相应的高炔丙胺，产率良好。