亚烷基类卡宾重排中炔烃迁移的机理方面。

Mechanistic aspects of alkyne migration in alkylidene carbenoid rearrangements.

作者信息

Bichler Paul, Chalifoux Wesley A, Eisler Sara, Shi Shun Annabelle L K, Chernick Erin T, Tykwinski Rik R

机构信息

Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G 2G2 Canada.

出版信息

Org Lett. 2009 Feb 5;11(3):519-22. doi: 10.1021/ol8023665.

DOI:10.1021/ol8023665

PMID:19128149

Abstract

The mechanism of the Fritsch-Buttenberg-Wiechell rearrangement of (13)C labeled precursors has been examined to determine the propensity of the alkynyl (R-CC-) group to migrate in an alkylidene carbenoid species. Reaction of dibromoolefins with n-BuLi and ketones with Me(3)SiC(Li)N(2) both demonstrate that the alkynyl moiety readily undergoes 1,2-migration from carbenoid intermediates.

摘要

已对（13）C标记前体的弗里奇-布滕贝格-维歇尔重排机制进行了研究，以确定炔基（R-CC-）基团在亚烷基类卡宾物种中迁移的倾向。二溴烯烃与正丁基锂以及酮与三甲基硅基叠氮化锂的反应均表明，炔基部分很容易从类卡宾中间体进行1,2-迁移。