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Co-Catalyzed Asymmetric Hydrogenation. The Same Enantioselection Pattern for Different Mechanisms.

ABSTRACT: The mechanism of the recently reported catalyzed asymmetric hydrogenation of enyne 1 catalyzed by the Co-(R,R)-QuinoxP* complex was studied by DFT. Conceivable pathways for the Co(I)-Co(III) mechanism were computed together with a Co(0)-Co(II) catalytic cycle. It is commonly assumed that the exact nature of the chemical transformations taking place along the actually operating catalytic pathway determine the sense and level of enantioselection of the catalytic reaction. In this work, two chemically different mechanisms reproduced the experimentally observed perfect stereoselection of the same handedness. Moreover, the relative stabilities of the transition states of the stereo induction stages were controlled via exactly the same weak disperse interactions between the catalyst and the substrate.

SUBMITTER: Gridnev ID

PROVIDER: S-EPMC10057697 | biostudies-literature | 2023 Mar

REPOSITORIES: biostudies-literature

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Co-Catalyzed Asymmetric Hydrogenation. The Same Enantioselection Pattern for Different Mechanisms.

Gridnev Ilya D ID

International journal of molecular sciences 20230314 6

The mechanism of the recently reported catalyzed asymmetric hydrogenation of enyne 1 catalyzed by the Co-(R,R)-QuinoxP* complex was studied by DFT. Conceivable pathways for the Co(I)-Co(III) mechanism were computed together with a Co(0)-Co(II) catalytic cycle. It is commonly assumed that the exact nature of the chemical transformations taking place along the actually operating catalytic pathway determine the sense and level of enantioselection of the catalytic reaction. In t ...[more]

PMID: 36982642

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