Faculté des sciences

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

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

In: Chemical Physics Letters, 2005, vol. 406 (4-6), p. 355-359

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... Plus

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    Summary
    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.