Harnessing Alkyl C–X Synthons for Constructing Vicinal Complexity via Alkene Radical Cations
Year: 2026
Type: preprint
Abstract: 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.’
Source: ChemRxiv
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
Awards: G1732709109, Track 4: Advanced CI Coordination Ecosystem: Monitoring and Measurement Services, Track 1: ACCESS Resource Allocations Marketplace and Platform Services (RAMPS), G4090037298, ACO: An Open CI Ecosystem to Advance Scientific Discovery (OpenCI), Track 3: COre National Ecosystem for CyberinfrasTructure (CONECT), G5097243881, G560129009, G63540804, Track 2: Customized Multi-tier Assistance, Training, and Computational Help (MATCH) for End User ACCESS to CI, Mechanistic Investigation into Modern Catalytic Reactions
OpenAlex ID: W7118424349