Work

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

Year: 2020

Type: article

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.

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.0c09575

Authors: Alexander Q. Cusumano, William A. Goddard, Brian M. Stoltz

Institution: California Institute of Technology

Language: English

Topic: Organometallic Complex Synthesis and Catalysis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: California Institute of Technology, National Institute of General Medical Sciences, Division of Chemical, Bioengineering, Environmental, and Transport Systems

Awards: The Synthesis of Bioactive Polycyclic Natural Products, G5258027049, G78455326