General Synthesis of N -Trifluoromethyl Compounds with N -Trifluoromethyl Hydroxylamine Reagents.

N -CF 3 compounds constitute valuable targets in medicinal chemistry. Extensive studies have been reported for the preparation of N -CF 3 compounds through fluorination and trifluoromethylation of N-containing compounds. The development of new synthetic methods from abundant and easily available substrates is highly desirable but still challenging. Herein, we report the design and synthesis of novel N -Cbz- and N -Boc- N -trifluoromethyl hydroxylamine reagents by silver-mediated oxidative trifluoromethylation. These reagents have been successfully applied to the direct incorporation of a NCF 3 moiety into the commonly used unsaturated substrates under photoredox catalysis. This protocol enables the efficient and regioselective C-H trifluoromethylamination of various (hetero)arenes, including complex bioactive molecules. Furthermore, a variety of alkenes, dienes, and isonitriles undergo tandem trifluoromethylamination/functionalization delivering structurally diverse N -trifluoromethyl aliphatic and heteroaromatic amines. Notably, previously unknown cyclic N -CF 3 compounds including N -CF 3 oxazolidinones and oxazolones were conveniently prepared with N -Boc- N -trifluoromethyl hydroxylamine reagents. Furthermore, diversification of the resulting α-trifluoromethylamino ketones afforded the largely underexplored N -alkenyl- and N -alkynyl- N -CF 3 compounds.