Iron-Catalyzed Allylic C-H Amination of Substituted 1,3-Dienes

A catalytic method for the selective allylic C-H amination of dienes and trienes using arylhydroxylamines has been developed. This iron-catalyzed approach involves the in situ generation of activated nitrosoarenes, which in turn react with dienes or trienes to give the corresponding aminomethyl dienes or trienes as the major products, and hetero-Diels-Alder adducts as minor products. The selectivity depends on the structures of both the catalyst and the substrate. We have also studied substituent effects using p-substituted phenylhydroxylamines.