1,3-Dipolar cycloaddition of nitrile imines with α,β-unsaturated lactones, thiolactones and lactams: synthesis of ring-fused pyrazoles

Abstract

1,3-Dipolar cycloaddition of nitrile imines with α,β-unsaturated five- and six-membered lactones, thiolactones and lactams gave ring-fused pyrazoles. Regioisomeric mixtures have been obtained with the 5-substituted pyrazole as the major cycloadduct. Only with the five-membered lactone the major product was the 4-acyl derivative. Computational studies, the use of the topological analysis of the Fukui functions and the potential energy surfaces (PES) theory allowed a theoretical description of the local reactivity in agreement with the observed high regiochemistry and with the role of the heteroatom adjacent to the carbonyl group.