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 non-adjacent 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.