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Journal of the Mexican Chemical Society

Print version ISSN 1870-249X

J. Mex. Chem. Soc vol.49 n.2 México  2005

 

Article

 

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 Herreraa,b, Hugo A. Jiménez-Vázquez*,a, Francisco Delgadoa, Björn C. G. Söderbergc and Joaquín Tamariz*,a

 

a Departamento de Química Orgánica, Escuela Nacional de Ciencias Biológicas, Instituto Politécnico Nacional, Prol. Carpio y Plan de Ayala, 11340 México, D.F., Mexico. * e-mail: jtamariz@woodward.encb.ipn.mx

b Instituto de Investigaciones Quimicobiológicas, Universidad Michoacana de San Nicolás de Hidalgo, Edif. B-1, Ciudad Universitaria, Francisco J. Mujica S/N, 58066 Morelia, Mich., Mexico

c C. Eugene Bennett Department of Chemistry, West Virginia University, P.O. Box 6045, Morgantown, West Virginia 26506-6045, USA

 

Received: November 4, 2004
Published on the web: April 12, 2005

 

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 n 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.

Keywords: captodative olefins, Friedel-Crafts, Diels-Alder cycloaddition, transition state calculations

 

Resumo

As olefinas captodativas 3a e 3b derivadas dos ácidos metacrílico e trans-crotônico foram preparadas. A presença de uma segunda ligação dupla na molécula, atuando como marcador interno, permitiu-nos comparar sua reatividade relativa em reações de Diesl-Alder e Friedel-Crafts. A reatividade foi avaliada com ciclopentadieno (6) atuando como dieno em cicloadição Diels-Alder, e com furano (9) e tiofeno (10) como substratos heteroaromáticos Friedel-Crafts. Em ambos os processos, a ligação dupla da enona captodativa mostrou-se mais reativa que a do sistema acrílico. A teoria FMO considera essa quimiosseletividade como consequência da maior contribuição da enona ao orbital LUMO dessas moléculas. A pequena seletividade exo observada na cicloadição com 6 concorda com a maior estabilidade do estado de transição, de acordo com os resultados de cálculos B3LYP/6-311G(d,p).

 

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Acknowledgments

We thank Fernando Labarrios for his help in spectrometric measurements. J.T. gratefully acknowledges DEPI/IPN (Grant 200410) and CONACYT (Grants 1570P-E9507 and 32273-E) for financial support; and he thanks OAS (F54111), CONACYT (250099), and COFAA-IPN (9711220214) for support during a sabbatical leave in USA. H.A.J.-V. thanks CONACYT (Grant 3251P) for financial support. R.H. is grateful to CONACYT for a graduate scholarship (91187), and to PIFI-IPN and the Ludwig K. Hellweg Foundation for partial scholarships. H.A.J.-V. and J.T. are fellows of the EDI/IPN and COFAA/IPN programs.

 

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