Cyclic vinyl p-tolyl sulfilimines as chiral dienophiles: Theoretical study on the stereoselectivity, Lewis acid catalysis, and solvent effects in their Diels-Alder reactions

José L. García Ruano, Fernando R. Clemente, Lorena González Gutiérrez, Ruth Gordillo, Ana M. Martín Castro, Jesús H. Rodríguez Ramos

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Abstract

The theoretical study reported in the present work deals with chiral cyclic vinyl sulfilimines and their reactivity as dienophiles in [4 + 2] cycloaddition reactions, using B3LYP/6-31G(d)//AM1 and B3LYP/6-31G(d)//B3LYP/6-31G(d) model chemistries. Consideration of Lewis acid catalysis, illustrated by BF3, decreases the activation energies of the cycloaddition process while the charge transfer from the diene to the sulfilimine is augmented. The [4 + 2] cycloaddition reactions of sulfilimines with both furan and cyclopentadiene occur in the gas phase with endo stereoselectivity, which is more pronounced with the latter diene. Endo-exo energy differences in the gas phase with the B3LYP/6-31+G(d)//B3LYP/6-31+G(d), B3LYP/6-31G(d)//B3LYP/6-31G(d), and B3LYP/6-31G-(d)//AM1 model chemistries are almost the same. Solvent effects are responsible for the inversion of the stereoselectivity in the reactions of sulfilimines with furan because of the great difference in the dipole moments in endo and exo approaches.

Original languageEnglish (US)
Pages (from-to)2926-2933
Number of pages8
JournalJournal of Organic Chemistry
Volume67
Issue number9
DOIs
Publication statusPublished - May 3 2002

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ASJC Scopus subject areas

  • Organic Chemistry

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