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

Abstract

The fundamental step responsible for enantioinduction in the inner-sphere asym. 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 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 aromaticity. We connect these findings to ubiquitous bonding concepts, such as Frontier MO theory and valence bonding theory.