7463-95-8Relevant academic research and scientific papers
Reactivity and endo-exo selectivity in Diels-Alder reaction of o- quinodimethanes. An experimental and DFT computational study
Di Valentin, Cristiana,Freccero, Mauro,Sarzi-Amadè, Mirko,Zanaletti, Riccardo
, p. 2547 - 2559 (2000)
endo-exo Selectivity in Dieis-Alder cycloadditions of several o- quinodimethanes (1-4) with acrylonitrile, 2-(5H)-furanone and N- methylmaleimide has been investigated in acetonitrile solution. Transition structures of the cycloaddition of the parent o-QDM (1), (E,E)-1,8-dimethyl- o-QDM (2), isoindene (3) and 2,3-dihydronaphthalene (4) with acrylonitrile and maleimide were located at both HF/6-31G* and B3LYP/6-31G* methods. Theoretical data reproduce fairly well both experimental absolute reaction rates and diastereoisomer ratios. The high endo selectivity has been rationalized mainly as a result of solvation effects (acetonitrile, PCM model) and reactant deformations. The latter is due to steric interactions. (C) 2000 Elsevier Science Ltd.
