Aryne formation via the hexadehydro Diels-Alder reaction and their Ritter-type transformations catalyzed by a cationic silver complex

Despite their electrophilic nature, arynes are not known to react with nitriles under typical conditions for their formation. We demonstrated, however, that structurally diverse arynes could be generated via the hexadehydro Diels-Alder reaction and trapped with nitriles to induce the Ritter-type reaction when catalyzed by a cationic silver species. Presumably, under these conditions, the transiently formed arynesilver complexes react with nitriles initially to form nitrilium ion intermediates, which then subsequently react with either water or carboxylic acid to yield the observed arylamides or arylimides. (C) 2017 Elsevier Ltd. All rights reserved.