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

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.