偕二（硅基）烯醛：基于阴离子接力化学，立体选择性合成 C3,O1-二硅烷基烯丙醇的多功能骨架。

Geminal bis(silyl) enal: a versatile scaffold for stereoselective synthesizing C3,O1-disilylated allylic alcohols based upon anion relay chemistry.

机构信息

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

出版信息

Org Lett. 2013 Mar 1;15(5):1104-7. doi: 10.1021/ol400145z. Epub 2013 Feb 15.

DOI:10.1021/ol400145z

PMID:23410199

Abstract

Geminal bis(silyl) enal 2a is shown to be a useful scaffold for anion relay chemistry (ARC) aimed at the stereoselective synthesis of C(3),O(1)-disilylated allylic alcohols. The ARC reaction is initiated by the addition of an alkyllithium to the aldehyde and features a CuCN-promoted C(sp2)-to-O 1,4-silyl migration to generate a vinylcuprate that reacts with activated electrophiles.

摘要

双(硅基)烯丙醛 2a 被证明是阴离子中继化学 (ARC) 的有用骨架，旨在立体选择性合成 C(3)、O(1)-二硅烷基烯丙醇。ARC 反应由烷基锂加成到醛中引发，并具有 CuCN 促进的 C(sp2)-到-O 1,4-硅基迁移，生成与活化亲电试剂反应的乙烯基铜。