Palladium-Catalyzed Asymmetric Benzylic Substitution of Secondary Benzyl Carbonates with Nitrogen and Oxygen Nucleophiles

A Pd/(R)-BINAP-catalyzed asymmetric benzylic substitution
of secondary benzyl carbonates with amides and amines proceeds to
form the corresponding optically active benzylamines in good yields
with a high enantiomeric ratio. The reaction occurs in a dynamic kinetic
asymmetric transformation (DYKAT) manner. Additionally, the asymmetric
Pd catalysis can also be applicable to phenol nucleophiles, thus delivering
chiral ethers with acceptable yields and enantioselectivity.