Enantioselective Nickel‐Catalyzed Hydrosilylation of 1,1‐Disubstituted Allenes

Abstract Here, we report the first example of Ni‐catalyzed asymmetric hydrosilylation of 1,1‐disubstituted allenes with high level of regioselectivities and enantioselectivities. The key to achieve this stereoselective hydrosilylation reaction was the development of the SPSiOL‐derived bisphosphite ligands (SPSiPO). This protocol features broad substrate scope, excellent functional group, and heterocycle tolerance, thus provides a versatile method for the construction of enantioenriched tertiary allylsilanes in a straightforward and atom‐economic manner. DFT calculations were performed to reveal the reaction mechanism and the origins of the enantioselectivity.