Regiodivergent cation sampling for distal Csp3 -functionalization

Despite notable progress in catalytic olefin isomerization processes enabling distal Csp3 -H functionalization, most methods depend on complex metal-based catalytic systems and face inherent challenges in achieving regiodivergent outcomes1–3 . Herein, we present a conceptually distinct approach in which we leverage cationic olefin isomerization for regiodivergent Csp³–H functionalization, wherein the selectivity results from a ketone-assisted process we term “cation sampling” . This method enables site-selective, on-demand regiodivergent functionalization of Csp³ carbons, allowing the formation of C– heteroatom bonds in challenging positions and unlocking access to products that were previously unattainable through metal-based methodologies. Remarkably, this platform is not limited to olefinic substrates, also offering a versatile framework for alcohol transposition reactions, a formal migratory Appel reaction, and an effective solution for resolving regioisomeric bromohydrin mixtures.