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Published November 11, 2020 | Supplemental Material + Accepted Version
Journal Article Open

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


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.

Additional Information

© 2020 American Chemical Society. Received: September 6, 2020; Published: October 27, 2020. We thank Professor Kendall Houk (UCLA) for insightful discussion. The Caltech High Performance Computing (HPC) center is acknowledged for support of computational resources. We thank the NIH (R01 GM080269), NSF (CBET-1805022), NSF (CBET-2005250), and Caltech for financial support. The authors declare no competing financial interest.

Attached Files

Accepted Version - nihms-1748570.pdf

Supplemental Material - ja0c09575_si_001.mp4

Supplemental Material - ja0c09575_si_002.xlsx

Supplemental Material - ja0c09575_si_003.pdf


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August 20, 2023
October 20, 2023