Direct intramolecular double cross-dehydrogentive-coupling (CDC) cyclization of N-(2-pyridyl)amidines under metal-free conditions

Abstract

A facile transition-metal-free protocol to form 2-iminoimidazo[1, 2-a]-pyridines bearing a –CHBr₂ group and an aza-quaternary carbon center at the 3 position from N-(2-pyridyl)amidines substrates, in which the new heterocyclic skeletons constructed from amidines via radical reactions or nucleophilic substitution reactions are promoted only by CBr₄ under mild conditions, is demonstrated. The reactions were realized by intramolecular CDC reaction involving C–N and C–C bond formation via the sequential C(sp³)–H bifunctionalization mode on the same carbon atom under mild conditions. Moreover, this work also provides an excellent and representative example for CBr₄ as an efficient reagent to initiate radical reactions under initiator-free conditions or to give rise to nucleophilic substitution reactions only by base.