Photoinduced Amination of α-CF3 Alkyl Bromides with Oxime Carbonates by Merging Energy Transfer and Boryl Radical-Mediated Halogen-Atom Transfer

Herein, we report a metal-free photoinduced amination of α-CF3 alkyl bromides with oxime carbonates, providing a broad scope of structurally diverse α-trifluoromethyl amines. Oxime carbonates function as bifunctional reagents that undergo homolysis to generate iminyl radicals as nitrogen sources and alkoxycarbonyloxyl radicals via an energy transfer (EnT) process. The alkoxycarbonyloxyl radicals abstract hydrogen atoms from ligated boranes via a hydrogen-atom transfer (HAT) process, yielding reactive ligated boryl radicals (LBRs) that trigger halogen-atom transfer (XAT).