Substitution Pattern‐Selective Olefin Cross‐Couplings

Abstract

AbstractThe use of radical ions as reactive intermediates can complement polarity‐driven and neutral radical‐driven reactions in synthetic organic chemistry. The present study revealed that the reactivity of enol ether radical cations can be simply tuned by addition/removal of a methyl group, allowing development of unique substitution pattern‐selective olefin cross‐couplings. Anodically generated enol ether radical cations selectively add to appropriately substituted alkenes to afford the corresponding cycloadducts in good‐to‐excellent yields. Competition experiments using alkenes possessing two differently substituted double bonds clearly demonstrated the unique reactivity of the enol ether radical cations.