How important are the intermolecular hydrogen bonding interactions in methanol solvent for interpreting the chiroptical properties?

Autor: Polavarapu PL; Department of Chemistry, Vanderbilt University, Nashville, TN 37235, USA. Electronic address: prasad.l.polavarapu@vanderbilt.edu., Santoro E; Department of Chemistry, Vanderbilt University, Nashville, TN 37235, USA., Covington CL; Department of Chemistry, Vanderbilt University, Nashville, TN 37235, USA; Department of Chemistry, Austin Peay State University, Clarksville, TN 37044, USA., Johnson JL; Department of Chemistry, Vanderbilt University, Nashville, TN 37235, USA., Puente AR; Department of Chemistry, Vanderbilt University, Nashville, TN 37235, USA., Schley ND; Department of Chemistry, Vanderbilt University, Nashville, TN 37235, USA. Electronic address: nathan.schley@vanderbilt.edu., Kallingathodi Z; Institute for Integrated Programmes and Research in Basic Sciences, Mahatma Gandhi University, Kottayam 686560, India., Prakasan PC; Institute for Integrated Programmes and Research in Basic Sciences, Mahatma Gandhi University, Kottayam 686560, India., Haleema S; Institute for Integrated Programmes and Research in Basic Sciences, Mahatma Gandhi University, Kottayam 686560, India., Thomas AA; Institute for Integrated Programmes and Research in Basic Sciences, Mahatma Gandhi University, Kottayam 686560, India., Ibnusaud I; Institute for Integrated Programmes and Research in Basic Sciences, Mahatma Gandhi University, Kottayam 686560, India. Electronic address: i.ibnusaud@gmail.com.
Jazyk: angličtina
Zdroj: Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy [Spectrochim Acta A Mol Biomol Spectrosc] 2021 Feb 15; Vol. 247, pp. 119094. Date of Electronic Publication: 2020 Oct 22.
DOI: 10.1016/j.saa.2020.119094
Abstrakt: Two crispine A analogs and tetrahydrofuro[2,3-b]furan-3,3a(6aH)-diol, endowed with hydroxyl groups that can participate in intramolecular hydrogen bonding, have been synthesized and experimental vibrational circular dichroism (VCD) spectra and optical rotatory dispersion (ORD) data have been measured in CD 3 OD/CH 3 OH solvents. The absolute configurations (ACs) of these compounds have been determined using their synthetic schemes, supplemented wherever possible with X-ray diffraction data. The ACs are also analyzed with quantum chemical (QC) calculations of VCD and ORD utilizing implicit solvation as well as explicit solvation models, with the later employing classical molecular dynamics (MD) simulations. It is found that VCD calculations with implicit solvation model are adequate for determining the ACs, despite propensity of studied compounds for intermolecular hydrogen bonding between solute and solvent molecules. This observation is important because time-consuming MD simulations may not be necessary in the type of situations studied here. Additionally, it is found that the QC predicted VCD spectra provided enough diastereomer discrimination for determining the correct AC of studied compounds independently. The same observation did not apply to ORD.
Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
(Copyright © 2020 Elsevier B.V. All rights reserved.)
Databáze: MEDLINE
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