Energy-Transfer-Mediated Radical-Relay Brook Rearrangement of Electron-Deficient Ketones

Herein, we report an energy transfer (EnT)-mediated radical-relay Brook rearrangement starting from commercially available electron-deficient ketones and silanes. This method eliminates the need for pre-installed α-silyl groups by employing an engineered N-O reagent that mediates a cascade of silane activation, regioselective carbonyl addition, and radical-radical cross-coupling. The orchestrated radical-involved cascade sequence exhibits a broad substrate scope and excellent functional group tolerance. Moreover, this protocol enables the late-stage diversification of complex drug molecules, offering a new paradigm for photochemistry.