Nickel-Hydride-Catalyzed Hydroalkylation of Cyclic Phosphinates: Generation of Enantioenriched Phosphorus and Carbon Stereocenters

In contrast to numerous examples leveraging Ni–H catalysis for the construction of a single or two adjacent stereocenters, accessing two stereoenriched 1,3-chiral centers has so far remained underexplored. Furthermore, Ni–H chemistry is yet to be extended beyond the construction of chirality at carbon. Herein, we report a Ni–H catalyzed dynamic kinetic asymmetric transformation of cyclic phosphinates, furnishing compounds with two nonadjacent stereocenters. Interconversion of P-chiral substrate enantiomers is achieved by fast and reversible migration of the alkene double bond, resulting in high levels of reaction enantio-, diastereo- and regioselectivity.