Ni-catalyzed asymmetric C-P cross-coupling reaction via Ni(I)/Ni(III) two-electron pathway

Nickel demonstrates excellent performance in C-C or C-X cross-coupling reactions involving a SET process. However, the Ni(I)/Ni(III) two-electron pathway, which does not require light irradiation, is still rare, particularly in the asym-metric version. Here, we disclose a Ni(II)-catalyzed asymmetric C-P cross-coupling reaction via the Ni(I)/Ni(III) two-electron redox pathway. Combined experimental and computational research reveals that Ni(II) can be readily reduced to Ni(0) by secondary phosphine oxides, resulting in the formation of a Ni(I) active catalyst through comproportiona-tion. The discovery of the Ni(I)/Ni(III) two-electron mechanism may serve as a new paradigm of Ni catalysis, offering exciting opportunities in asymmetric reactions complementary to the traditional SET process.