Regioselective Access to α-Vinylsilanes and α-Vinylgermanes by Cobalt-Catalyzed Migratory Hydrofunctionalization of 2-Alkynes

被引：29

作者：

Sahoo, Manoj Kumar ^{[1
,2
]}

Kim, Dongwook ^{[1
,2
]}

Chang, Sukbok ^{[1
,2
]}

Park, Jung-Woo ^{[1
,2
]}

机构：

[1] Inst Basic Sci IBS, Ctr Catalyt Hydrocarbon Functionalizat, Daejeon 34141, South Korea

[2] Korea Adv Inst Sci & Technol KAIST, Dept Chem, Daejeon 34141, South Korea

来源：

ACS CATALYSIS | 2021年 / 11卷 / 20期

关键词：

cobalt; alkyne; hydrosilylation; hydrogermanylation; pi-bond migration; MARKOVNIKOV HYDROSILYLATION; ALKYNE HYDROSILYLATION; TRIFLUOROMETHYLATED ALKYNES; ALLENE HYDROSILYLATION; HYDROGERMYLATION; COMPLEXES; REGIO; CONVERSION; SILICON;

D O I：

10.1021/acscatal.1c03769

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

While migratory functionalization of alkynes has been recognized as a unique way to access allylic functionalities via pi-allyl metal intermediates, hydrofunctionalization of pi-alkynes to afford alpha-functional olefins has been unexplored. We describe herein the use of a cobalt hydride based system for regioselective migratory hydrofunctionalization of 2-alkynes to furnish alpha-vinylsilanes and alpha-vinylgermanes by a mechanistic understanding of the cobalt hydride species on alkyne pi-bond migration. The key mechanism of alkyne pi-bond migration by [bis(dicyclohexylphosphino)ethane]cobalt hydride is strongly supported by both experimental and computational studies, and the role of each reaction component, such as alkynes and silanes, is elucidated to rationalize the unique alpha-vinyl selectivity.

引用

页码：12777 / 12784

页数：8

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