Synergistic Diselenide/Guanidine Catalyzed Dehydrophosphorylation of 2-Nitrobenzhydrols to Access C-Stereogenic Phosphinates

Abstract

The development of catalytic and eco-friendly P-umpolung strategy for the synthesis of chiral phosphorus-containing compounds presents substantial challenges. Herein, we report a method for accessing C-stereogenic phosphinates enabled by a synergistic diselenide/chiral guanidine catalytic system. This method avoids stoichiometric halogenating reagents, generating water as the sole byproduct. Mechanistic studies reveal that the electron-deficient diselenide catalyst catalyzes phosphorus polarity inversion, while the chiral guanidine activates the alcohol via Brønsted base catalysis. This strategy effectively achieves the kinetic resolution of secondary alcohols with similar steric substituents, offering a sustainable strategy to access phosphinates with stereogenic benzhydryl groups.