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Title: Prediction of enhanced solvent-induced enantioselectivity for a ring opening with a bifurcating reaction path

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/C4CP05078A· OSTI ID:1233171
 [1];  [2];  [3]
  1. Cardiff Univ., Cardiff (United Kingdom)
  2. KU Leuven, Heverlee (Belgium)
  3. Univ. of Bristol, Bristol (United Kingdom); Stanford Univ., Stanford, CA (United Kingdom); SLAC National Accelerator Lab., Menlo Park, CA (United States)
+ Show Author Affiliations

Classical molecular dynamics simulations are reported for the deazetisation and ring opening of meso-2,3-difluoro-2,3-dimethyldiazocyclopropane in three solvents: CHCl3, CHFClBr and CH3CH(OH)CF3 (TFIPA). In this study, the achiral reactant leads to enantiomeric allene products, and the question addressed in the study is whether either of the chiral, enantiomerically pure solvents can induce significant enantiomeric excess in the products. The direct dynamics calculations use an empirical valence bond potential for the solute, with empirical parameters optimised against M06-2X/cc-pVTZ density functional results. The results reveal that the exothermic N2 loss and ring opening promote transient strong solvent–solute interactions within the first ~100 fs of the reaction. Because of the bifurcating reaction path, these interactions occur at time when the “decision” about which enantiomer of the product to form has yet to be made (at least for many of the trajectories). Hence, it is possible in principle that the solvent could exert a larger-than-normal influence on the course of the reaction. In fact, the results reveal no such effect for CHFClBr but do predict that TFIPA should induce 15.2 ± 2.1% enantiomeric excess. This is roughly an order of magnitude larger than solvent-induced enantiomeric excesses found experimentally in reactions where the conversion of reactant(s) to enantiomeric products occur over separate transition states.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
EP/K000489/1; EP/L005913/1; AC03-76SF00515
OSTI ID:
1233171
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Vol. 17, Issue 13; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 43 works
Citation information provided by
Web of Science

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Re-Evaluating the Transition State for Reactions in Solution: Re-Evaluating the Transition State for Reactions in Solution journal November 2018
Reactive molecular dynamics: From small molecules to proteins journal August 2018
Reactive force fields made simple journal January 2015
EVB and polarizable MM study of energy relaxation in fluorine–acetonitrile reactions journal January 2019
Post-transition state bifurcations induce dynamical detours in Pummerer-like reactions journal January 2018
Low dimensional representations along intrinsic reaction coordinates and molecular dynamics trajectories using interatomic distance matrices journal January 2019
Sampling reactive regions in phase space by following the minimum dynamic path journal February 2019
Post-transition state bifurcations gain momentum – current state of the field journal June 2017
Capturing the Role of Explicit Solvent in the Dimerization of Ru V (bda) Water Oxidation Catalysts journal May 2017
Low Dimensional Representations along Intrinsic Reaction Coordinates and Molecular Dynamics Trajectories Using Interatomic Distance Matrices posted_content June 2019
Sampling Reactive Regions in Phase Space by Following the Minimum Dynamic Path text January 2019
Sampling Reactive Regions in Phase Space by Following the Minimum Dynamic Path text January 2019
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