Photoredox Activation of Donor-Acceptor Cyclopropanes: Distonic Radical Cation Reactivity in [3+2] Cycloaddition Reactions

Altering the reactivity model of a molecule can potentially eliminate limitations existing in its current paradigm. When it comes to the activation of Donor-Acceptor Cyclopropanes (DACs), Lewis acids have been the state-of-the-art. Although a variety of polarized 2 pi components have been successfully coupled with DACs for [3+2] cycloaddition, unpolarized alkenes prove to be a roadblock due to an inherent polarity mismatch with the Lewis acid-mediated 1,3-zwitterionic intermediate. Hereby, harnessing the distonic radical cation mode of cleavage by photoredox catalysis overcomes this mismatched reactivity of the zwitterionic intermediate, providing a unique route to highly substituted cyclopentanes and cyclopentenes. Expansion of this strategy to bicyclo[1.1.0]butanes enables access to bicyclo[3.1.1]heptanes (BCHs) through a facile [3 sigma+2 sigma] cycloaddition. Detailed mechanistic insights are also provided using dispersion-corrected density functional theory.