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. Here we report the palladium‐catalyzed stereoselective cleavage of a C−P bond for the construction of atropisomers bearing a P‐stereogenic center. The products are isolated in high yields with high diastereo‐ and enantioselectivities (>25 : 1 dr and up to 98 % ee). One of the isolated products is shown to catalyze the [3+2] cycloaddition of allenoates to imines, thus demonstrating the utility of the present methodology.