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An Ionic Liquid Dependent Mechanism for Base Catalyzed β‑Elimination Reactions from QM/MM Simulations

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journal contribution
posted on 23.01.2013, 00:00 by Caley Allen, Somisetti V. Sambasivarao, Orlando Acevedo
Ionic liquids have been proposed to induce a mechanistic change in the reaction pathway for the fundamentally important base-induced β-elimination class compared to conventional solvents. The role of the reaction medium in the elimination of 1,1,1-tribromo-2,2-bis­(3,4-dimethoxyphenyl)­ethane via two bases, piperidine and pyrrolidine, has been computationally investigated using methanol and the ionic liquids 1-butyl-3-methylimidazolium tetrafluoroborate and hexafluorophosphate [BMIM]­[BF4] and [BMIM]­[PF6], respectively. QM/MM Monte Carlo simulations utilizing free-energy perturbation theory found the ionic liquids did produce a reaction pathway change from an E1cB-like mechanism in methanol to a pure E2 route that is consistent with experimental observations. The origin of the ionic liquid effect has been found as: (1) a combination of favorable electrostatic interactions, for example, bromine-imidazolium ion, and (2) π–π interactions that enhance the coplanarity between aromatic rings maximizing the electronic effects exerted on the reaction route. Solute–solvent interaction energies have been analyzed and show that liquid clathrate solvation of the transition state is primarily responsible for the observed mechanistic changes. This work provides the first theoretical evidence of an ionic liquid dependent mechanism and elucidates the interplay between sterics and electrostatics crucial to understanding the effect of these unique solvents upon chemical reactions.