(Aminomethyl)pyridine Complexes for the Cobalt-Catalyzed Anti-Markovnikov Hydrosilylation of Alkoxy- or Siloxy(vinyl)silanes with Alkoxy- or Siloxyhydrosilanes

被引：40

作者：

Lee, Kangsang L. ^{[1
]}

机构：

[1] Dow Chem Co USA, Core R&D, 2200 West Salzburg Rd, Auburn, MI 48611 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2017年 / 56卷 / 13期

关键词：

alkoxysilanes; alkoxy(vinyl)silanes; cobalt catalysis; hydrosilylation; siloxanes; DEHYDROGENATIVE SILYLATION; ALKENE HYDROSILYLATION; IRON CATALYSTS; STEREOSELECTIVE HYDROSILYLATION; TERTIARY SILANES; NICKEL-COMPLEXES; SILICON HYDRIDES; POLYMERIZATION; HYDROSILATION; MECHANISM;

D O I：

10.1002/anie.201612460

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Cobalt-catalyzed anti-Markovnikov reactions that involve siloxy-or alkoxy(vinyl) silanes and siloxy- or alkoxy-hydrosilanes are disclosed. More than 25 new cobalt-(amino-methyl) pyridine complexes were developed as catalysts for the hydrosilylation of industry-relevant and challenging siloxy-or alkoxy-terminated vinylsilanes. These transformations typically proceed in the presence of 0.25 mol% of the cobalt complex with 0.75 mol% of the alkylating agent to afford the desired products in up to > 98% yield with > 98% antiMarkovnikov selectivity in 30 min. The current protocol shows a broad substrate scope, delivering more than 25 siloxanes with siloxy or alkoxy functional groups at both termini, and can also be applied to polymeric vinyl-and hydrosiloxanes.

引用

页码：3665 / 3669

页数：5