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

Abstract A rhodium(III)‐catalyzed redox‐neutral C−H and C−C bond activation reaction of aryl oximes and CF 3 ‐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(sp 2 )–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.