Hydrogen bond stabilization in Diels–Alder transition states: The cycloaddition of hydroxy-ortho-quinodimethane with fumaric acid and dimethylfumarate

Tamilmani, Venkatachalam; Daul, Claude; Lage Robles, Jaime; Bochet, Christian G.; Venuvanalingam, P.

doi:10.1016/j.cplett.2005.03.017

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Journal article

Hydrogen bond stabilization in Diels–Alder transition states: The cycloaddition of hydroxy-ortho-quinodimethane with fumaric acid and dimethylfumarate

Tamilmani, Venkatachalam Department of Chemistry, University of Fribourg, Switzerland - Department of Chemistry, Bharathidasan University, Tiruchirappalli, Tamil Nadu, India
Daul, Claude Department of Chemistry, University of Fribourg, Switzerland
Lage Robles, Jaime Department of Chemistry, University of Fribourg, Switzerland
Bochet, Christian G. Department of Chemistry, University of Fribourg, Switzerland
Venuvanalingam, P. Department of Chemistry, Bharathidasan University, Tiruchirappalli, Tamil Nadu, India

25.03.2005

Published in:

Chemical Physics Letters. - 2005, vol. 406, no. 4, p. 355-359

English DFT investigations on the mechanism of Diels–Alder reactions of a hydroxy-ortho-quinodimethane with fumaric acid derivatives were performed to understand the origin of the syn or anti configuration of the adducts. The diene hydroxyl group and the dieneophile carboxyl group show hydrogen bonding in the transition state, significantly favouring the syn product. This reaction is poorly diastereoselective for R = CO₂Me (ratio syn/anti = 57:43) and significantly improved for R = CO₂H (ratio syn/anti = 71:29). The stereoselectivities are properly predicted from transition structures calculated at the B3LYP/6-31G(d) level.

Faculty

Faculté des sciences et de médecine

Department

Département de Chimie

Language