Contractions of 1,4-Diazepines to Pyrroles Triggered by Valence Tautomerization: A One-Pot Approach and Mechanism.

ABSTRACT

Herein, we describe the valence tautomerizations of fused 1,4-diazepines, which are reconstructed to give pyrrole derivatives and HCN gas. Several factors that influence the equilibrium between each valence tautomer of an 8π-electron diazepine skeleton are demonstrated. On the basis of these mechanistic studies, a cascade strategy for the construction of diazepines followed by ring contraction is developed to afford aryl- or alkyl-substituted pyrrolo[1,2-a]quinolines that are otherwise challenging to fabricate. In addition, further transformations of the obtained products highlight the advantages of the developed methodology.