Kinetic and computational analysis of the palladium(II)-catalyzed asymmetric allylic trichloroacetimidate rearrangement: development of a model for enantioselectivity |
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Authors: | Watson Mary P Overman Larry E Bergman Robert G |
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Institution: | Department of Chemistry, 1102 Natural Sciences II, University of California, Irvine, California 92697-2025, USA. |
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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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