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

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.