Diels-Alder Reaction in Water. Effects of Hydrophobicity and Hydrogen Bonding

Article abstract of DOI:10.1021/jo00097a045

In order to check whether the activated complex for the Diels-Alder reactions of 5-substituted 1,4-naphthoquinones 1a-e with cyclopentadiene (2) is more polar in water than in other solvents, we have determined the substituent effects in seven different solvents.The substituent effects gradually decrease with increasing rate of the reaction in a specific solvent, indicating that the charge separation in the activated complex in water is not much different from that in the other solvents.We also compared solvent effects on the Diels-Alder reaction of methyl vinyl ketone (3) with cyclopentadiene with effects on the corresponding reaction of methyl vinyl sulfone (4).The medium effects were separated into effects on initial state and activated complex.The destabilization of the initial state by water and the stabilization of the activated complex by 2,2,2-trifluoroethanol were less pronounced for the sulfone than for the ketone.These results further underline the importance of enforced hydrophobic interactions and changes in hydrogen bonding during the activation process in explaining the acceleration of Diels-Alder reactions in water.