The fundamental step responsible for enantioinduction in the inner-sphere asymmetric Tsuji allylic alkylation is C–C bond formation through a unique seven-membered pericyclic transition state. We investigate how the electronic structure of the transition metal center enables the C–C bond forming process. Phase inversion introduced by <i>d</i> 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 aromaticity.  We connect these findings to ubiquitous bonding concepts, such as Frontier Molecular Orbital theory and valence bonding theory.

Reductive elimination from palladium(II) via a [π2s + π2s + σ2s + σ2s] pericyclic reaction

ACS Fall 2021

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