Unexpected Role of Zinc Hydride in Catalytic Hydrosilylation of Ketones and Nitriles

被引：71

作者：

Boone, Courtney ^{[1
]}

Korobkov, Ilia ^{[2
]}

Nikonov, Georgii I. ^{[1
]}

机构：

[1] Brock Univ, Dept Chem, St Catharines, ON L2S 3A1, Canada

[2] Univ Ottawa, Fac Sci, Xray Core Facil, Ottawa, ON K1N 6N5, Canada

来源：

ACS CATALYSIS | 2013年 / 3卷 / 10期

基金：

加拿大自然科学与工程研究理事会;

关键词：

hydrosilylation; zinc hydride; mechanism; nitrile; ketone; SOLUBLE CALCIUM HYDRIDE; ASYMMETRIC HYDROSILYLATION; CARBONYL-COMPOUNDS; B(C6F5)(3)-CATALYZED HYDROSILYLATION; ENANTIOSELECTIVE HYDROSILYLATION; CHIRAL LIGANDS; REDUCTION; COMPLEXES; MECHANISM; POLYMETHYLHYDROSILOXANE;

D O I：

10.1021/cs400581w

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：

The hydride compound DippNacNacZnH (1) catalyzes chemoselective hydrosilylation of ketones and aldehydes under mild conditions and chemoselective reduction of nitrites to imines. Mechanistic studies showed that the product of nitrile insertion into the Zn-H bond of 1, DippNacNacZn-N=C(H)(Ph) (2), is not a potent catalyst. Kinetic studies under catalytic conditions suggest a reversible, coordination of silane to 1 to form an intermediate which then reacts with the substrate (nitrile or ketone) via a cyclic, transition state to give the silylated product.

引用

页码：2336 / 2340

页数：5

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