通过亲电硅氢键活化实现镍催化的末端烯烃与伯硅烷的硅氢化反应
Nickel-Catalyzed Hydrosilylation of Terminal Alkenes with Primary Silanes via Electrophilic Silicon-Hydrogen Bond Activation.
作者信息
Wu Xiaoyu, Ding Guangni, Lu Wenkui, Yang Liqun, Wang Jingyang, Zhang Yuxuan, Xie Xiaomin, Zhang Zhaoguo
机构信息
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
出版信息
Org Lett. 2021 Feb 19;23(4):1434-1439. doi: 10.1021/acs.orglett.1c00111. Epub 2021 Jan 30.
We report a simple and effective nickel-based catalytic system, NiCl·6HO/BuOK, for the electrophilically activated hydrosilylation of terminal alkenes with primary silanes. This protocol provides excellent performance under mild reaction conditions: exclusive anti-Markovnikov selectivity, broad functional group tolerance (36 examples), and good scalability (TON = 5500). However, the secondary and tertiary silanes are not suitable. Mechanistic studies revealed that this homogeneous catalytic hydrosilylation includes an electrophilically activated Si-H bond process without the generation of nickel hydrides.
我们报道了一种简单有效的镍基催化体系NiCl·6H₂O/BuOK，用于末端烯烃与伯硅烷的亲电活化硅氢化反应。该方法在温和的反应条件下具有出色的性能：具有专一的反马氏选择性、广泛的官能团耐受性（36个实例）以及良好的可扩展性（TON = 5500）。然而，仲硅烷和叔硅烷并不适用。机理研究表明，这种均相催化硅氢化反应包括一个亲电活化的Si-H键过程，且不生成氢化镍。
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