6533b835fe1ef96bd129f317

RESEARCH PRODUCT

Understanding the role of the Lewis acid catalyst on the 1,3-dipolar cycloaddition of N-benzylideneaniline N-oxide with acrolein: a DFT study

Wafaa BenchoukSidi Mohamed MekellecheLuis R. Domingo

subject

NucleophileChemistryComputational chemistryOrganic ChemistryDrug DiscoveryElectrophile13-Dipolar cycloadditionLewis acids and basesSolvent effectsBiochemistryPolarizable continuum modelCycloadditionLewis acid catalysis

description

Abstract The Lewis acid (LA) catalyzed 1,3-dipolar cycloaddition of N -benzylideneaniline N -oxide with acrolein has been studied using DFT calculations. Coordination of AlCl 3 to the acrolein oxygen atom produces a drastic change in the mechanism along the more favorable meta reactive channel. The process is characterized by a strong nucleophile/electrophile interaction allowing the formation of a zwitterionic intermediate, a Michael-type addition. The subsequent ring closure constitutes the rate-determining step. The energies obtained with the inclusion of solvent effect by means of the polarizable continuum model are in good agreement with experimental findings. Analysis of the global and local electrophilicity allows to explain correctly the reactivity and regioselectivity of the LA catalyzed cycloaddition.

yearjournalcountryeditionlanguage
2007-05-01Tetrahedron
https://doi.org/10.1016/j.tet.2007.03.064