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.

与诸多利用镍氢（Ni–H）催化构建单个或两个相邻手性中心的研究案例相比，迄今针对立体富集的1,3-手性中心的构建仍未得到充分探索。此外，镍氢化学的应用范畴尚未拓展至碳手性中心构建以外的领域。本文报道了一种镍氢催化的环状次膦酸酯动态动力学不对称转化反应，可得到含有两个非相邻手性中心的产物。通过烯烃双键的快速可逆迁移，能够实现P-手性底物对映异构体之间的互变，进而使反应展现出优异的对映选择性、非对映选择性与区域选择性。