Related Experiment Video
Updated: Oct 9, 2025

Unraveling Entropic Rate Acceleration Induced by Solvent Dynamics in Membrane Enzymes
Published on: January 16, 2016
Effect of solvent motions on the dynamics of the Diels-Alder reaction
Xiaoyong Zhang1, Pierre-Louis Lefebvre1,2, Jeremy N Harvey1
1Theoretical and Computational Chemistry, Department of Chemistry, KU Leuven Celestijnenlaan 200F, 3001, Leuven, Belgium. jeremy.harvey@kuleuven.be.
Abstract:
How solvent motions affect the dynamics of chemical reactions in which the solute undergoes a substantial shape change is a fundamental but elusive issue. This work utilizes reactive simulation and Grote-Hynes theory to explore the effect of solvent motions on the dynamics of the Diels-Alder reaction (in the reverse direction, this reaction involves very substantial solute expansion) in aprotic solvents. The results reveal that the solvent environment is not sufficiently constraining to influence transition state passage dynamics, with the calculated transmission coefficients being close to unity. Even when solvent motions are suppressed or artificially slowed down, the solvent only affects the reaction dynamics in the transition state region to a very small extent. The only notable effect of solvent occurs far from the transition state region and corresponds to caging of the reactants within the reactant well.
Related Concept Videos
Diels–Alder vs Retro-Diels–Alder Reaction: Thermodynamic Factors
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
Diels–Alder Reaction: Characteristics of Dienes
Characteristics of the diene
Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is...
Diels–Alder Reaction: Characteristics of Dienophiles
Characteristics of Dienophiles
Generally, the best dienophiles are alkenes containing electron-withdrawing substituents such as carbonyl, nitrile, and nitro groups. The feasibility of a Diels–Alder reaction depends...
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry

