Cymantrene-based iminodiamidophosphites: the first phosphite-type ligands with planar chirality

Optically active phosphite-type ligands with planar chirality have been synthesized for the first time. The new cymantrene-based P,N-iminodiamidophosphites demonstrated high enantioselectivity in the Pd-catalyzed allylic substitution of 1,3-diphenylallyl acetate with dimethyl malonate (up to 94% ee), pyrrolidine (up to 78% ee) and sodium para-toluene sulfinate (up to 84% ee).