Nickel-Catalyzed Regioselective Dihydrosilylation of Allenes

Herein, we report a nickel-catalyzed regioselective dihydrosilylation of allenes to access 1,3-bis(silane)s bearing two remote silyl groups. Enabled by a commercially available diphosphine ligand (Xantphos), this method proceeds under mild conditions with exclusive regioselectivity, a broad substrate scope, and excellent functional group tolerance. Mechanistic studies support a two-step sequence involving an initial branch-selective hydrosilylation, followed by a linear-selective hydrosilylation of the resulting terminal alkene. 1,3-Bis(silane)s could undergo orthogonal transformations into a variety of 1,3-difunctionalized molecules and participate in Pt-catalyzed hydrosilylation polymerization with dialkynes, highlighting the potential of this structural motif in both synthetic chemistry and materials science.