Chemoselective Alkene Hydrosilylation Catalyzed by Nickel Pincer Complexes
Chemoselective Alkene Hydrosilylation Catalyzed by Nickel Pincer Complexes
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DOI：
10.1002/anie.201507829
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发表时间：
2015-11-23
影响因子：
16.6
通讯作者：
Hu, Xile
中科院分区：
文献类型：
--
作者：
Buslov, Ivan;Becouse, Jeanne;Hu, Xile
使用贱金属催化剂难以实现官能化烯烃的化学选择性氢化硅烷化。本文报道的是，明确定义的双（氨基）酰胺镍钳形络合物是用于末端烯烃的反马尔可夫氢化硅烷化的有效催化剂，其具有高达83000/小时的转换频率和高达10000的转换数。含有氨基、酯、酰氨基、酮和甲酰基的烯烃被选择性氢化硅烷化。反应条件的轻微改变允许使用这些镍催化剂的内烯烃的串联异构化/氢化硅烷化反应。
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 83000 per hour and turnover numbers of up to 10000. 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.