Palladium-Catalyzed Stereoselective Cleavage of C−P Bond: Enantioselective Construction of Atropisomers Containing a P-Stereogenic Center

Abstract

The transition-metal-catalyzed C−P bond cleavage has emerged as a powerful tool for the formation of both C−C and C−P bond. However, the transition-metal-catalyzed stereoselective cleavage of C−P bond is still undeveloped. Herein, we report a palladium-catalyzed stereoselective cleavage of C−P bond for the construction of P-stereogenic phosphines and stereogenic axis. This protocol enables the quick synthesis of atropisomers bearing a P-stereogenic center in high yields, diastereo- and enantioselectivities of up to 98 % ee, >25 : 1 dr. The product is able to serve as chiral catalyst in phosphine catalyzed [3+2] cycloaddition of allenoates to imines, showing the great potential of the present methodology.