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Treatment of tert-butyl isonitrile with ArSO2NBr2 and nitrile led to simultaneous C–N single bond scission of isonitrile and migration of tert-alkyl group to nitrogen centre of the nitrile precursor, resulting in the formation of N-sufonyl amidine.

Stereoselective synthesis of (Z)‐3‐methyleneisoindolin‐1‐one has been achieved via intermolecular coupling of terminal alkynes and 2‐halobenzamide using a square pyramidal [Cu(DMAP)4I]I complex as catalyst within a short time. This cross coupling reaction features the use of unprotected 2‐halobenzamide to achieve excellent yield of corresponding isoindolin‐1‐ones with free NH group. The catalyst was also found to be equally active for N‐substituted 2‐halobenzamide, phenyl propiolic acids and silylated alkyne.

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