Nickel-Catalyzed Hydrosilylation of Terminal Alkenes with Primary Silanes via Electrophilic Silicon-Hydrogen Bond Activation

Xiaoyu Wu; Guangni Ding; Wenkui Lu; Liqun Yang; Jingyang Wang; Yuxuan Zhang; Xiaomin Xie; Zhaoguo Zhang

doi:10.1021/acs.orglett.1c00111

Nickel-Catalyzed Hydrosilylation of Terminal Alkenes with Primary Silanes via Electrophilic Silicon-Hydrogen Bond Activation

Org Lett. 2021 Feb 19;23(4):1434-1439. doi: 10.1021/acs.orglett.1c00111. Epub 2021 Jan 30.

Authors

Xiaoyu Wu¹, Guangni Ding¹, Wenkui Lu¹, Liqun Yang¹, Jingyang Wang¹, Yuxuan Zhang¹, Xiaomin Xie¹, Zhaoguo Zhang^{1

2}

Affiliations

¹ 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.
² State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.

PMID: 33522233
DOI: 10.1021/acs.orglett.1c00111

Abstract

We report a simple and effective nickel-based catalytic system, NiCl₂·6H₂O/^tBuOK, 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.