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The Transition Metal Catalyzed [π2s + π2s + σ2s + σ2s] Pericyclic Reaction: Woodward-Hoffmann Rules, Aromaticity, and Electron Flow.

ABSTRACT: We have shown that the fundamental step responsible for enantioinduction in the inner-sphere asymmetric Tsuji allylic alkylation is C-C bond formation through a seven-membered pericyclic transition state. We employ an extensive series of quantum mechanics (QM) calculations to delineate how the electronic structure of the Pd-catalyzed C-C bond forming process controls the reaction. Phase inversion introduced by d orbitals renders the Pd-catalyzed [π2s + π2s + σ2s + σ2s] reaction symmetry-allowed in the ground state, proceeding through a transition state with Craig-Möbius-like σ-aromaticity. Lastly, we connect QM to fundamental valence bonding concepts by deriving an ab initio "arrow-pushing" mechanism that describes the flow of electron density through the reaction.

SUBMITTER: Cusumano AQ

PROVIDER: S-EPMC8549492 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature

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The Transition Metal Catalyzed [π2s + π2s + σ2s + σ2s] Pericyclic Reaction: Woodward-Hoffmann Rules, Aromaticity, and Electron Flow.

Cusumano Alexander Q AQ Goddard William A WA Stoltz Brian M BM

Journal of the American Chemical Society 20201027 45

We have shown that the fundamental step responsible for enantioinduction in the inner-sphere asymmetric Tsuji allylic alkylation is C-C bond formation through a seven-membered pericyclic transition state. We employ an extensive series of quantum mechanics (QM) calculations to delineate how the electronic structure of the Pd-catalyzed C-C bond forming process controls the reaction. Phase inversion introduced by d orbitals renders the Pd-catalyzed [π2s + π2s + σ2s + σ2s] reaction symmetry-allowed ...[more]

PMID: 33107727

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