ABSTRACT
The enantioselectivity of the nickel-catalyzed, asymmetric hydrocyanation of vinylarenes using glucose-derived, chiral phosphinite ligands, L, increased dramatically when the ligands contained electron-withdrawing meta phosphorus-aryl substituents. Mechanism studies implicate a NiL(vinylarene) complex as the active catalyst and suggest that the rate of reductive elimination of product from a NiL(η3-aryl)CN complex increases relative to (J-hydride elimination as the electron-withdrawing power of the phosphorus-aryl substituent increases.
