An Easily Accessed Nickel Nanoparticle Catalyst for Alkene Hydrosilylation with Tertiary Silanes

The first efficient and non‐precious nanoparticle catalyst for alkene hydrosilylation with commercially relevant tertiary silanes has been developed. The nickel nanoparticle catalyst was prepared in situ from a simple nickel alkoxide precatalyst Ni(OtBu)2⋅x KCl. The catalyst exhibits high activity for anti‐Markovnikov hydrosilylation of unactivated terminal alkenes and isomerizing hydrosilylation of internal alkenes. The catalyst can be applied to synthesize a single terminal alkyl silane from a mixture of internal and terminal alkene isomers, and to remotely functionalize an internal alkene derived from a fatty acid.