4,4‘-Disubstituted BINAPs for Highly Enantioselective Ru-Catalyzed Asymmetric Hydrogenation of Ketones

A family of tunable precatalysts Ru(4,4‘-BINAP)(chiral diamine)Cl2 was synthesized and used for highly enantioselective hydrogenation of
aromatic ketones. This result differs from previous chiral diphosphines that rely on the bis(xylyl)phosphino groups to control enantioselectivity.
An X-ray structural study reveals that the bulky substituents on the 4,4‘-positions of BINAP can effectively create a suitable chiral pocket in
the transition state and thus provide a new mechanism for the enantiocontrol in such a remarkable asymmetric catalytic process.