Asymmetric Synthesis of P-Stereogenic Secondary Phosphine-Boranes by an Unsymmetric Bisphosphine Pincer-Nickel Complex

The first highly enantioselective catalytic synthesis of P-stereogenic secondary phosphine-boranes was realized by the asymmetric addition of primary phosphine to electron-deficient alkenes with a newly developed unsymmetric bisphosphine (PCP') pincer-nickel complex. Various P-stereogenic secondary phosphine-boranes were obtained in 57-92% yields with up to 99% ee and >20:1 dr. The follow-up alkylation upon P-C bond formation with alkyl halides provided a practical way to access P-chiral compounds with diverse functional groups.

Automated summary

The first highly enantioselective catalytic synthesis of P-stereogenic secondary phosphine-boranes was achieved using a newly developed unsymmetric bisphosphine pincer-nickel complex. Various P-stereogenic secondary phosphine-boranes were obtained in good yields with high enantioselectivity and diastereoselectivity. Subsequent alkylation upon P-C bond formation provided a practical way to access P-chiral compounds with diverse functional groups.