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
-
- English
- Classification
- Chemistry
- License
- License undefined
- Identifiers
-
- RERO DOC 4462
- DOI 10.1016/j.cplett.2005.03.017
- Persistent URL
- https://folia.unifr.ch/unifr/documents/299574
Statistics
Document views: 67
File downloads:
- 1_bochet_hbs.pdf: 131