Kinetic and Computational Analysis of the Palladium(II)-Catalyzed Asymmetric Allylic Trichloroacetimidate Rearrangement: Development of a Model for Enantioselectivity

The asymmetric rearrangement of allylic trichloroacetimidates catalyzed by palladium(II)
complexes of the COP family is a powerful method for the preparation of enantioenriched chiral allylic
amines from prochiral allylic alcohols. A detailed kinetic analysis of this reaction was performed to elucidate
the rate- and enantiodetermining step of this important reaction. The results of these studies support a
cyclization-induced rearrangement mechanism and prompted DFT studies (B3LYP/LACVP**+) of C−N
bond formation, believed to be the enantiodetermining step of this catalytic cycle. On the basis of these
calculations, a model for enantioinduction was developed, in which the planar chirality of the catalyst controls
the enantioselectivity. These studies should allow the rational design of more enantioselective catalysts.