Jump to main content
Jump to site search

Issue 13, 2015
Previous Article Next Article

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

Author affiliations

Abstract

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). 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.

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

Back to tab navigation

Supplementary files

Publication details

The article was received on 03 Nov 2014, accepted on 10 Dec 2014 and first published on 11 Dec 2014


Article type: Paper
DOI: 10.1039/C4CP05078A
Citation: Phys. Chem. Chem. Phys., 2015,17, 8372-8381
  • Open access: Creative Commons BY license
  •   Request permissions

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

    B. K. Carpenter, J. N. Harvey and D. R. Glowacki, Phys. Chem. Chem. Phys., 2015, 17, 8372
    DOI: 10.1039/C4CP05078A

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements