Asymmetric Access to Phosphinates via Nickel-Catalyzed Hydrophosphorylation of Alkynes

In spite of broad applications of P-chiral phosphinates, the related asymmetric synthesis still faces significant challenges. Compared with traditional methods, transition-metal-catalyzed asymmetric synthesis has emerged as a more efficient approach for constructing P-chiral compounds. However, for the asymmetric synthesis of phosphinates, current strategies predominantly rely on using noble metal catalysts and usually suffer from low enantioselectivity. Here we report a simple nickel-catalyzed hydrophosphorylation of unactivated alkynes, enabling the highly regioselective and enantioselective synthesis of P-chiral phosphinates. The yields and enantiomeric excess (ee) values can reach up to 95% and 94%, respectively, with a broad functional group tolerance. A gram-scale-up reaction is conducted, and the double bond in the product can be easily modified. Mechanistic studies including isotopic labeling experiments and DFT calculations support a proposed reaction mechanism.