Nature Study Enables Ketone Annulation Despite 1-Volt Redox Disadvantage

2 articles · Updated · Nature.com · Jul 15

Researchers report a new outer-sphere single-electron-transfer selectivity model that enables radical annulation of difficult-to-reduce cyclopropyl ketones with easier-to-reduce alkenes.
Super-potent photoreductants drive diffusion-limited electron transfer, making substrate redox potentials largely irrelevant and shifting selectivity to competition between downstream chemistry and back electron transfer.
The team says the approach works even when the needed ketone reduction is disfavored by 1 volt, a mismatch that had previously blocked such coupling reactions.
Published in Nature, the work positions indiscriminate photoreduction as a broader blueprint for designing SET reactions that must override conventional redox-potential control.