Iodine ate complexes and N-lithiobenzocyclobutenamine intermediates in the reactions of α-lithionitriles with benzyne

α-Lithionitriles add to benzynes to give N-lithiobenzocyclobutenamines in a two-step process. The intermediate aryllithiums can be trapped prior to cyclization with iodobenzene or 2,6-dimethoxyiodobenzene to form iodine-ate complex intermediates which fragment preferentially to 2-(α-cyanobenzyl)-iodobenzenes. The N-lithiobenzocyclobutenamines undergo ring opening to yield either 2-substituted benzonitriles or α-substituted benzylcyanides depending on the substitution pattern on the aryl and cyclobutene rings.