Nickel/Bronsted acid dual-catalyzed regio- and enantioselective hydrophosphinylation of 1,3-dienes: access to chiral allylic phosphine oxides

While chiral allylic organophosphorus compounds are widely utilized in asymmetric catalysis and for accessing bioactive molecules, their synthetic methods are still very limited. We report the development of asymmetric nickel/Bronsted acid dual-catalyzed hydrophosphinylation of 1,3-dienes with phosphine oxides. This reaction is characterized by an inexpensive chiral catalyst, broad substrate scope, and high regio- and enantioselectivity. This study allows the construction of chiral allylic phosphine oxides in a highly economic and efficient manner. Preliminary mechanistic investigations suggest that the 1,3-diene insertion into the chiral Ni-H species is a highly regioselective process and the formation of the chiral C-P bond is an irreversible step.

Automated summary

The study introduces a novel asymmetric nickel/Bronsted acid dual-catalyzed reaction for the synthesis of chiral allylic phosphine oxides, featuring economic efficiency, broad substrate scope, and high selectivity. Preliminary mechanistic investigations suggest a highly regioselective process for 1,3-diene insertion into chiral Ni-H species and an irreversible step for chiral C-P bond formation.