Harnessing Alkyl C–X Synthons for Constructing Vicinal Complexity via Alkene Radical Cations

In organic chemistry, 1,2-difunctionalization strategies are reliant on the use of vicinal carbon functional groups, most notably, alkenes. Herein, we report an exergonic activation mode that directly generates alkene radical cation intermediates from monofunctional C(sp³)–X handles via a concerted hydrogen-atom abstraction and spin-center shift process. This catalytic platform allows us to develop a suite of transformations that depart from current conventional synthetic logic for which alkyl C–X scaffolds are confined to single-site substitutions, now transforming them into nonintuitive precursors for building vicinal complexity. Incorporation of the spin-center shift process in the platform ultimately allows for transfer of electrophilic reactivity from one carbon to another, allowing for the establishment of a new synthetic concept – ‘electrophilic shuttling.’