Thermal and Sc(OTf)3 catalyzed 1,3-dipolar cycloaddition of open-chain nitrones to α,β-unsaturated lactones: combined experimental and computational studies

Abstract

The stereoselectivity of 1,3-dipolar cycloaddition reactions of C-phenyl open-chain nitrones and α,β-unsaturated γ- and δ-lactones was investigated under thermal and catalytic conditions. It was found that under thermal conditions, the endo approach of the reactants was preferred leading to the thermodynamic product. In the presence of Sc(OTf)3 the exo adduct was obtained in high yield and selectivity. The energies of the cycloaddition reactions were investigated by means of molecular orbital calculations at the B3LYP/6-31+G(d,p) and MP3/6-31+G(d,p) theory level. Different reaction channels and reactant approaches, fitting the individual regio- and stereochemical preferences, are discussed. The computational results were compared with the corresponding experimental data and found to be in good agreement.