Laboratory of Inorganic Synthesis and Catalysis, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne (EPFL), ISCI-LSCI, BCH 3305, 1015 Lausanne (Switzerland) http://lsci.epfl.ch.
Angew Chem Int Ed Engl. 2015 Nov 23;54(48):14523-6. doi: 10.1002/anie.201507829. Epub 2015 Oct 2.
Chemoselective hydrosilylation of functionalized alkenes is difficult to achieve using base-metal catalysts. Reported herein is that well-defined bis(amino)amide nickel pincer complexes are efficient catalysts for anti-Markovnikov hydrosilylation of terminal alkenes with turnover frequencies of up to 83,000 per hour and turnover numbers of up to 10,000. Alkenes containing amino, ester, amido, ketone, and formyl groups are selectively hydrosilylated. A slight modification of reaction conditions allows tandem isomerization/hydrosilylation reactions of internal alkenes using these nickel catalysts.
使用基础金属催化剂很难实现官能化烯烃的化学选择性氢化硅烷化反应。本文报道了，结构明确的双（氨基）酰胺镍夹持配合物是末端烯烃反马氏加成氢化硅烷化反应的有效催化剂，其每小时的周转频率高达 83,000，周转数高达 10,000。含有氨基、酯基、酰胺基、酮基和甲酰基的烯烃被选择性地氢化硅烷化。稍微改变反应条件，就可以使用这些镍催化剂进行内部烯烃的串联异构化/氢化硅烷化反应。
