Activated vinylcyclopropanes (VCPs) can form zwitterionic π-allylmetal species in the presence of transition metals and are widely used in organic synthesis. A nickel-catalyzed asymmetric allylation of secondary phosphine oxide with...

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.

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An asymmetric arylation of H-phosphinates with aromatic iodo or bromo compounds, catalyzed by cheap and easily available nickel(II) salts, provides access to P-stereogenic phosphinates. This method features mild reaction conditions and a good functional-group compatibility that includes aniline and phenol derivatives.

Nickel performs excellently in C–C and C–X cross-coupling reactions. Here, we disclose a Ni(II)-catalyzed asymmetric C–P cross-coupling reaction to afford valuable chiral heterocyclic tertiary phosphine oxides. The method is mild and efficient, which invokes a self-sustained nickel catalytic cycle without an external reductant, light irradiation, or electricity.