Rh(III)‐Catalyzed C(sp2)–H and C(sp2)–C(sp2) Bond Activation of Aryl Oximes with CF3‐Imidoyl Sulfoxonium Ylides: Access to N‐(2‐Cyanoaryl)‐3‐(Trifluoromethyl)isoquinolin‐1(2H)‐Imines

A rhodium(III)‐catalyzed redox‐neutral C‐H and C‐C bond activation reaction of aryl oximes and CF3‐substituted imidoyl sulfoxonium ylides (TFISYs) has been described, producing a wide variety of N‐(2‐cyanoaryl)‐3‐(trifluoromethyl)isoquinolin‐1(2H)‐imines in moderate to excellent yields. The transformation might involve a consecutive C(sp2)–H bond activation, intramolecular spiro‐cyclization, C‐C bond activation and N‐O bond cleavage sequence. This developed protocol provides a direct entry to diverse trifluoromethyl and nitrile‐containing heterocycles with the generation of water and dimethyl sulfoxide as by‐products.