Electrophotochemical Ce-Catalyzed Radical Truce–Smiles Rearrangement of Cycloalkanols

The Truce-Smiles rearrangement enables access to arylethylamines in pharmaceuticals, yet typically requires amide substrates or prefunctionalized radical precursors. We report a redox-neutral electrophotochemical rearrangement of cycloalkanols catalyzed by inexpensive cerium salts. Alkoxy radicals are generated directly from unmodified alcohols via ligand-to-metal charge transfer, triggering β-scission and 1,4-aryl migration to furnish β-arylethylamines. The method avoids external oxidants, precious metals, and preinstalled radical handles, operating under mild conditions with broad scope, high functional-group tolerance, and scalability. Mechanistic experiments and computations reveal a Ce(III)/Ce(IV) catalytic cycle and radical <i>ipso</i> substitution through a spirocyclic dearomatized intermediate. This platform expands access to arylethylamines from cycloalkanols.