New Captodative Olefíns: 3-(2-Furoyloxy)-3-buten-2-one and Alkyl 2-(2-Furoyloxy)-2-propenoates, and their Reactivity in Addition Reactions
Blanca M. Santoyo,1 Rafael Herrera,2 Raúl Aguilar,1 Aydeé Fuentes-Benites,1,3 Fabiola Jiménez,1 and Joaquín Tamariz*1
1 Departamento de Química Orgánica, Escuela Nacional de Ciencias Biológicas, Instituto Politécnico Nacional, Prol. de Carpio y Plan de Ayala, 11340 México, D.F., México. Tels: (+5255) 5729-6300/62411; Fax: (+5255) 5729-6300/46211; jtamariz@woodward.encb.ipn.mx
2 Instituto de Investigaciones Quimicobiológicas, Universidad Michoacana de San Nicolás de Hidalgo, Edif. B-1, Ciudad Universitaria, Francisco J. Mújica S/N, 58066 Morelia, Mich., Mexico.
3 Departamento de Química Orgánica, Facultad de Química, Universidad Autónoma del Estado de México, Paseo Colón/Paseo Tollocan S/N, 50000 Toluca, Edo. de México, Mexico.
]]>Recibido el 14 de agosto de 2007
Aceptado el 1 de noviembre de 2007
Abstract
A new series de captodative olefins 3-(2-furoyloxy)-3-buten-2-one and alkyl 2-(2-furoyloxy)-2-propenoates, 3a-3c, has been prepared with the aim of evaluating the effect of a heterocycle in the electron-donating moiety on the reactivity of these compounds in Diels-Alder and conjugate additions. In the former reactions, their behavior has been evaluated by reacting under thermal and catalyzed conditions with cyclopentadiene (9) and cyclohexadiene (12) as the dienes, showing a comparable reactivity, but a lower stereoselectivity, with respect to the reference captodative olefins 1a and 2a. In the case of conjugate additions, the Friedel-Crafts reaction of the highly activated benzene ring of 1,2,4-trimethoxybenzene (7) led to the corresponding adduct 8 only for olefin 3a. Ab initio calculations (HF/6-31G*) of the energies and coefficients of the FMOs were carried out to explain the experimental reactivity in both processes. The results suggest that both the electron-withdrawing and the 2-furoyloxy groups are involved in controlling the reactivity and selectivity of olefins 3.
Keywords: Captodative olefins, 2-furoyloxy group, Diels-Alder, Friedel-Crafts, FMO.
Resumen
Se describe la preparación de una nueva serie de olefinas captodativas 3-(2-furoiloxi)-3-buten-2-ona y 2-(2-furoiloxi)-2-propenoatos de alquilo, 3a-3c, con el fin de evaluar el efecto del heterociclo en la parte electro-donadora de la olefina sobre su reactividad en reacciones de Diels-Alder y de adiciones conjugadas. En el primer caso, se evaluó su comportamiento bajo condiciones térmicas y catalizadas empleando ciclopentadieno (9) y ciclohexadieno (12) como los dienos, encontrándose una reactividad comparable, aunque menor estereoselectividad, con respecto a las olefinas captodativas de referencia 1a and 2a. Para el caso de la adición conjugada, la reacción de Friedel-Crafts del compuesto 1,2,4-trimetoxibenceno (7), el cual posee un anillo bencénico muy activado, condujo solamente al aducto correspondiente, 8, de la olefina 3a. Se llevaron a cabo cálculos ab initio (HF/6-31G*) de energías y coeficientes de los FMOs para explicar la reactividad experimental en ambos procesos. Estos resultados sugieren que la reactividad y selectividad de las olefinas 3 están controladas tanto por el grupo electroatractor como por el grupo 2-furoiloxi.
]]> Palabras clave: Olefinas captodativas, grupo 2-furoiloxi, Diels-Alder, Friedel-Crafts, OMF.
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Acknowledgments
We thank Dr. Hugo A. Jiménez Vázquez and Fernando Labarrios for their help in X-ray and spectrometric measurements. J.T. would like to acknowledge SIP-IPN (Grants 20030147, 20040123, and 20070339) and CONACYT (Grants 32273-E and 43508-Q) for financial support. B.M.S. A.F.B., and F.J. are grateful to CONACYT for graduate fellowships, and to the PIFI-IPN program for scholarships. B.M.S. also thanks the Ludwig K. Hellweg Foundation for a partial scholarship. J.T. is a fellow of the EDI/IPN and COFAA/IPN programs.
References and Notes
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