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  • Title: Kinetic and computational analysis of the palladium(II)-catalyzed asymmetric allylic trichloroacetimidate rearrangement: development of a model for enantioselectivity.
    Author: Watson MP, Overman LE, Bergman RG.
    Journal: J Am Chem Soc; 2007 Apr 25; 129(16):5031-44. PubMed ID: 17402733.
    Abstract:
    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.
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