Photocatalyzed Trifluoromethylamidative Ring Opening of Bicyclo[1.1.0]butanes: Access to Trifluoromethylamidyl Cyclobutenes

Abstract The trifluoromethylamination method has recently evolved as a powerful paradigm for preparing N-CF3 compounds, among which the NCF3 radical-transfer approach is of particular interest but remains underdeveloped. Here we report a photocatalyzed trifluoromethylamidative ring-opening reaction of donor–acceptor bicyclo[1.1.0]butanes (BCBs), delivering a range of inaccessible but valuable trifluoromethylamidyl cyclobutenes. The method expands the heteroatom-radical-mediated ring-opening reaction of BCBs and enables radical trifluoromethylamination at sp3 carbon, thereby challenging current addition reactions of NCF3 radical only with unsaturated molecules.