Intermolecular Enantiospecific Reductive C-P Bond Reorganization of Atropisomeric Bisphosphines with Alkynes via Nickel Catalysis

Abstract

Selective C–P bond activation of bisphosphines remains a major challenge in organophosphorus chemistry. Current strategies are largely restricted to intramolecular cyclization or require pre-activated substrates, while one-step intermolecular enantiospecific C–P functionalization of axially chiral bisphosphines has not been realized. Herein we report the first direct, intermolecular, enantiospecific reductive C–P bond reorganization of atropisomeric bisphosphines with alkynes via alcohol-assisted nickel catalysis. This single-step protocol provides rapid and divergent access to chiral P/olefin hybrid ligands and vinyl phosphine derivatives (67 examples in total, with ≥ 99% ee for the majority). The transformation proceeds via in situ generation of an alkenylalkoxy nickel species, which undergoes an unconventional reductive elimination involving a dative P–Ni interaction to deliver a phosphonium intermediate, thereby activating the otherwise inert C–P bond. This late-stage editing not only constitutes a versatile platform for expediting ligand library assembly and constructing P-containing bioactive molecules, but also establishes a new mechanistic paradigm for C–P bond functionalization.

Abstract as supplied by the indexing source. © the authors / publisher.