1-Acetylvinyl Acrylates: New Captodative Olefins Bearing an Internal Probe for the Evaluation of the Relative Reactivity of Captodative against Electron-Deficient Double Bonds in Diels-Alder and Friedel-Crafts Reactions


  • Rafael Herrera Instituto Politécnico Nacional
  • Hugo A. Jiménez Instituto Politécnico Nacional
  • Francisco Delgado Instituto Politécnico Nacional
  • Björn C. G. Söderber West Virginia University
  • Joaquín Tamariz Instituto Politécnico Nacional


Captodative olefins, Friedel-Crafts, Diels-Alder cycloaddition, state calculations


Abstract. The captodative olefins 1-acetylvinyl esters of methacrylic and trans-crotonic acids, 3a and 3b, have been prepared. The presence of a second double bond in the molecule, acting as an internal probe, allowed us to compare their relative reactivity in Diels-Alder and Friedel-Crafts reactions. The reactivity was evaluated with cyclopentadiene (6) as diene in Diels-Alder cycloadditions, and with furan (9) and thiophene (10) as heteroaromatic Friedel-Crafts substrates. In both processes, the captodative enone double bond proved to be more reactive than that in the acrylic moiety. FMO theory accounted for this chemoselectivity as a consequence of the major π contribution of the enone to the LUMO of these molecules. The slight exo stereoselectivity observed in the cycloaddition to 6 parallels the higher stability of the corresponding transition state, according to the results of B3LYP/6-311G(d,p) calculations.


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Author Biographies

Rafael Herrera, Instituto Politécnico Nacional

Departamento de Química Orgánica, Escuela Nacional de Ciencias Biológicas

Instituto de Investigaciones Quimicobiológicas, Universidad Michoacana de San Nicolás de Hidalgo

Hugo A. Jiménez, Instituto Politécnico Nacional

Departamento de Química Orgánica, Escuela Nacional de Ciencias Biológicas

Francisco Delgado, Instituto Politécnico Nacional

Departamento de Química Orgánica, Escuela Nacional de Ciencias Biológicas

Björn C. G. Söderber, West Virginia University

C. Eugene Bennett Department of Chemistry

Joaquín Tamariz, Instituto Politécnico Nacional

Departamento de Química Orgánica, Escuela Nacional de Ciencias Biológicas


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