title: The influence of solvation and finite temperatures on theWittig reaction: A theoretical study.
abstract: The effects of the solvent and finite temperature (entropy) on the Wittig reaction are studied by using density functional theory in combination with molecular dynamics and a continuum solvation model. Standard gas-phase zero-temperature calculations are found to give similar results to previous studies. Gas-phase dynamics simulations allow the free energy profile of the reaction to be calculated through thermodynamic integration. The free energy profile is found to have a significant entropic barrier to the addition step of the reaction where only a small barrier was present in the potential energy curve. The introduction of the solvent dimethyl sulfoxide causes a change in the structure of the intermediate from the oxaphosphetane structure to the dipolar betaine structure. The overall reaction energy is changed only slightly. When the effects of both entropy and the solvent are included a significant entropic barrier to the addition reaction is obtained and the predicted intermediate again has the betaine structure.
authors.affiliation: Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, AB T2N-1N4, Canada.
authors.forename: Michael
authors.initials: M
authors.lastname: Seth
authors.forename: Hans Martin
authors.initials: HM
authors.lastname: Senn
authors.forename: Tom
authors.initials: T
authors.lastname: Ziegler