醛、炔烃和二烷基硅烷的脱氢环缩合反应。

Dehydrogenative cyclocondensation of aldehydes, alkynes, and dialkylsilanes.

作者信息

Baxter Ryan D, Montgomery John

机构信息

Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109-1055, USA.

出版信息

J Am Chem Soc. 2008 Jul 30;130(30):9662-3. doi: 10.1021/ja803774s. Epub 2008 Jul 4.

DOI:10.1021/ja803774s

PMID:18598032

Abstract

The nickel-catalyzed coupling of aldehydes, alkynes, and dialkylsilanes results in an unusual dehydrogenative cyclocondensation process to afford five-membered silacyclic products. The process allows dialkylsilanes to serve as a silylene synthetic equivalent. A mechanistic pathway for the process involving the formation of an aldehyde/alkyne-derived nickel metallacycle followed by sequential sigma-bond metathesis processes involving the two Si-H bonds has been proposed.

摘要

镍催化的醛、炔烃和二烷基硅烷的偶联反应会产生一种不寻常的脱氢环缩合过程，从而得到五元硅环产物。该过程使二烷基硅烷可作为硅烯的合成等效物。有人提出了该过程的一种机理途径，即先形成醛/炔烃衍生的镍金属环，然后依次进行涉及两个Si-H键的σ键复分解过程。