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Chirality–Helicity Equivalence in the S and R Stereoisomers: A Theoretical Insight

  • Tianlv Xu
    Tianlv Xu
    Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research and Key Laboratory of Resource, National and Local Joint Engineering Laboratory for New Petro-chemical Materials and Fine Utilization of Resources, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081, China
    More by Tianlv Xu
    • , 
  • Jia Hui Li
    Jia Hui Li
    Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research and Key Laboratory of Resource, National and Local Joint Engineering Laboratory for New Petro-chemical Materials and Fine Utilization of Resources, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081, China
    More by Jia Hui Li
    • , 
  • Roya Momen
    Roya Momen
    Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research and Key Laboratory of Resource, National and Local Joint Engineering Laboratory for New Petro-chemical Materials and Fine Utilization of Resources, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081, China
    More by Roya Momen
    • , 
  • Wei Jie Huang
    Wei Jie Huang
    Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research and Key Laboratory of Resource, National and Local Joint Engineering Laboratory for New Petro-chemical Materials and Fine Utilization of Resources, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081, China
    More by Wei Jie Huang
    • , 
  • Steven Robert Kirk*
    Steven Robert Kirk
    Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research and Key Laboratory of Resource, National and Local Joint Engineering Laboratory for New Petro-chemical Materials and Fine Utilization of Resources, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081, China
    *[email protected]
    More by Steven Robert Kirk
    Orcidhttp://orcid.org/0000-0002-0462-6962
    • , 
  • Yasuteru Shigeta
    Yasuteru Shigeta
    Center for Computational Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8577, Japan
    More by Yasuteru Shigeta
    • , and 
  • Samantha Jenkins*
    Samantha Jenkins
    Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research and Key Laboratory of Resource, National and Local Joint Engineering Laboratory for New Petro-chemical Materials and Fine Utilization of Resources, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081, China
    *[email protected]
    More by Samantha Jenkins
    Orcidhttp://orcid.org/0000-0002-4288-7653
Cite this: J. Am. Chem. Soc. 2019, 141, 13, 5497–5503
Publication Date (Web):March 13, 2019
https://doi.org/10.1021/jacs.9b00823
Copyright © 2019 American Chemical Society
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Abstract

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We located the unknown chirality–helicity equivalence in molecules with a chiral center, and as a consequence, the degeneracy of the S and R stereoisomers of lactic acid was lifted. An agreement was found with the naming schemes of S and R stereoisomers from optical experiments. This was made possible by the construction of the stress tensor trajectories in a non-Cartesian space defined by the variation of the position of the torsional bond critical point upon a structural change, along the torsion angle, θ, involving a chiral carbon atom. This was undertaken by applying a torsion θ, −180.0° ≤ θ ≤ +180.0° corresponding to clockwise and counterclockwise directions. We explain why scalar measures can at best only partially lift the degeneracy of the S and R stereoisomers, as opposed to vector-based measures that can fully lift the degeneracy. We explained the consequences for stereochemistry in terms of the ability to determine the chirality of industrially relevant reaction products.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.9b00823.

  • QTAIM and stress tensor bond theoretical background; the variation of the relative energy ΔE with torsion θ; the procedure to generate the trajectory length Lσ and implementation details of the calculation of the eigenvector, following path lengths H and H*; tables of the stress tensor Uσ space trajectory lengths Lσ and real space trajectory lengths l in atomic units (a.u.) of the S and R stereoisomers; the variation of bond-path properties of the torsional C1–C2 BCP; the combined plots of bond-path properties of the torsion C1–C2 BCP; magnified (10×) versions of the bond-path set B{p, q, r} for the C1–C2 BCP; variations of the ellipticity ε with the distance along bond-path (r) of the torsion C1–C2 BCP corresponding to the relative energy ΔE extrema; the QTAIM and stress tensor properties of the S and R stereoisomers of alanine; the QTAIM and stress tensor properties of glycine (PDF)

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Cited By

This article is cited by 12 publications.

  1. Thomas Malcomson, Alireza Azizi, Roya Momen, Tianlv Xu, Steven R. Kirk, Martin J. Paterson, Samantha Jenkins. Stress Tensor Eigenvector Following with Next-Generation Quantum Theory of Atoms in Molecules: Excited State Photochemical Reaction Path from Benzene to Benzvalene. The Journal of Physical Chemistry A 2019, 123 (38) , 8254-8264. https://doi.org/10.1021/acs.jpca.9b07519
  2. Shuman Li, Alireza Azizi, Steven R. Kirk, Samantha Jenkins. An explanation of the unusual strength of the hydrogen bond in small water clusters. International Journal of Quantum Chemistry 2020, 120 (19) https://doi.org/10.1002/qua.26361
  3. Alireza Azizi, Roya Momen, Herbert Früchtl, Tanja Mourik, Steven R. Kirk, Samantha Jenkins. Next‐generation QTAIM for scoring molecular wires in E‐fields for molecular electronic devices. Journal of Computational Chemistry 2020, 41 (9) , 913-921. https://doi.org/10.1002/jcc.26137
  4. Tianlv Xu, Xin Bin, Steven R. Kirk, David J. Wales, Samantha Jenkins. Flip rearrangement in the water pentamer: Analysis of electronic structure. International Journal of Quantum Chemistry 2020, 120 (6) https://doi.org/10.1002/qua.26124
  5. Yanyu Huang, Yuanting Fu, Mengting Li, Dawei Jiang, Christopher J. Kutyreff, Jonathan W. Engle, Xiaoli Lan, Weibo Cai, Tianfeng Chen. Chirality‐Driven Transportation and Oxidation Prevention by Chiral Selenium Nanoparticles. Angewandte Chemie 2020, 132 (11) , 4436-4444. https://doi.org/10.1002/ange.201910615
  6. Yanyu Huang, Yuanting Fu, Mengting Li, Dawei Jiang, Christopher J. Kutyreff, Jonathan W. Engle, Xiaoli Lan, Weibo Cai, Tianfeng Chen. Chirality‐Driven Transportation and Oxidation Prevention by Chiral Selenium Nanoparticles. Angewandte Chemie International Edition 2020, 59 (11) , 4406-4414. https://doi.org/10.1002/anie.201910615
  7. Tian Tian, Tianlv Xu, Steven R. Kirk, Ian Tay Rongde, Yong Boon Tan, Sergei Manzhos, Yasuteru Shigeta, Samantha Jenkins. Intramolecular mode coupling of the isotopomers of water: a non-scalar charge density-derived perspective. Physical Chemistry Chemical Physics 2020, 22 (4) , 2509-2520. https://doi.org/10.1039/C9CP05879F
  8. Alireza Azizi, Roya Momen, Steven R. Kirk, Samantha Jenkins. 3-D bond-paths of QTAIM and the stress tensor in neutral lithium clusters, Li m ( m = 2–5), presented on the Ehrenfest force molecular graph. Physical Chemistry Chemical Physics 2020, 22 (2) , 864-877. https://doi.org/10.1039/C9CP05066C
  9. LiLing Wang, Alireza Azizi, Roya Momen, Tianlv Xu, Steven R. Kirk, Michael Filatov, Samantha Jenkins. Next‐generation quantum theory of atoms in molecules for the S 1 /S 0 conical intersections in dynamics trajectories of a light‐driven rotary molecular motor. International Journal of Quantum Chemistry 2020, 120 (1) https://doi.org/10.1002/qua.26062
  10. Tianlv Xu, Steven Robert Kirk, Samantha Jenkins. A comparison of QTAIM and the stress tensor for Chirality-Helicity equivalence in S and R stereoisomers. Chemical Physics Letters 2020, 738 , 136907. https://doi.org/10.1016/j.cplett.2019.136907
  11. Tianlv Xu, Roya Momen, Alireza Azizi, Tanja Mourik, Herbert Früchtl, Steven R. Kirk, Samantha Jenkins. The destabilization of hydrogen bonds in an external E‐field for improved switch performance. Journal of Computational Chemistry 2019, 40 (21) , 1881-1891. https://doi.org/10.1002/jcc.25843
  12. Shuman Li, Tianlv Xu, Tanja van Mourik, Herbert Früchtl, Steven R. Kirk, Samantha Jenkins. Halogen and Hydrogen Bonding in Halogenabenzene/NH3 Complexes Compared Using Next-Generation QTAIM. Molecules 2019, 24 (16) , 2875. https://doi.org/10.3390/molecules24162875

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