Abstract The chemoselectivity in the palladium-catalyzed intramolecular cyclization of 2-(o- bromoaryl)-alkenenitriles depends on the nature of α-substitutents. 2-(o-Bromoanilino) alkenenitriles attacked the cyano group, followed by the cyano group transposition and hydrolysis, to give o-(methylamino) benzonitrile. 2-(o-Bromobenzyl) alkenenitriles, 2-(o- bromophenylthio) alkenenitriles and 2-(o-bromophenoxy)-alkenenitriles attacked the ...