Pd(II)-Catalyzed Enantioselective C(sp³)–H Arylation toward P-Stereogenic Dialkylphosphinamides

Transition-metal-catalyzed enantioselective C–H functionalization has emerged as a promising method for the synthesis of P-stereogenic phosphorus compounds. However, previous reports are limited to the enantioselective functionalization of C(sp2)–H bonds of aryl phosphine derivatives. Herein, Pd(II)-catalyzed enantioselective arylation of more challenging C(sp3)–H bonds toward P-stereogenic dialkylphosphinamides is achieved through the desymmetrization of gem-diethyl groups. Various P-stereogenic dialkylphosphinamides are obtained with high enantioselectivities using 3,3′-CN2-H8-BINOL as the chiral ligand. The synthetic potential of this methodology is highlighted by gram-scale preparation and further derivatizations.