Formation of new pyridyl substituted enamines. Observation of a diaza-Cope rearrangement

Some 2-arylthiopyridinium imides when reacted with dimethyl acetylene dicarboxylate exhibited ambident behaviour: either a 1,3-dipolar cyclization occurred followed by a ring transformation to yield pyrrolopyridines or 5-pyridyl substituted enamines were formed in a different route. Mechanistic considerations revealed that this latter unusual transformation is initiated by a Michael addition of the imide nitrogen atom of the starting pyridinium compound on the reagent, which is followed by a [3,3]-sigmatropic ('diaza-Cope') rearrangement. Ring opening of the pyrrolopyridine compounds by a base also yielded pyridylenamines, which proved to be positional isomers of the sigmatropic rearrangement products. The new pyridyl derivatives seem to be valuable compounds for further transformations. Thus, they can undergo thermal electrocyclization to 7-azaindoles. (C) 2008 Elsevier Ltd. All rights reserved.