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Dissymmetry Factor Spectral Analysis Can Provide Useful Diastereomer Discrimination: Chiral Molecular Structure of an Analogue of (−)-Crispine A
[Image: see text] (1R,10bR)-1′-((R)-1,2-Dihydroxyethyl)-1-hydroxy-8,9-dimethoxy1,5,6,10b-tetrahydropyrrolo [2,1-a]isoquinolin-3(2H)-one, an analogue of (−)-crispine A, with three stereogenic centers is synthesized and its absolute configuration (AC) established using the combined information derived...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2019
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6648312/ https://www.ncbi.nlm.nih.gov/pubmed/31459760 http://dx.doi.org/10.1021/acsomega.8b03678 |
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author | Johnson, Jordan L. Nair, Divya Sadasivan Pillai, Sarath Muraleedharan Johnson, Didimos Kallingathodi, Zabeera Ibnusaud, Ibrahim Polavarapu, Prasad L. |
author_facet | Johnson, Jordan L. Nair, Divya Sadasivan Pillai, Sarath Muraleedharan Johnson, Didimos Kallingathodi, Zabeera Ibnusaud, Ibrahim Polavarapu, Prasad L. |
author_sort | Johnson, Jordan L. |
collection | PubMed |
description | [Image: see text] (1R,10bR)-1′-((R)-1,2-Dihydroxyethyl)-1-hydroxy-8,9-dimethoxy1,5,6,10b-tetrahydropyrrolo [2,1-a]isoquinolin-3(2H)-one, an analogue of (−)-crispine A, with three stereogenic centers is synthesized and its absolute configuration (AC) established using the combined information derived from the synthetic scheme and single crystal X-ray diffraction data. The experimental chiroptical spectra (namely, optical rotatory dispersion (ORD), electronic circular dichroism (ECD), and vibrational circular dichroism (VCD)) and the corresponding quantum chemical (QC) predicted spectra for all diastereomers are used to evaluate the AC. The AC of the synthesized compound could be correctly established using any one of the three chiroptical spectroscopic methods (ORD, ECD, or VCD) when the relative configuration is constrained to be that derived from X-ray data or when the ACs of two of the chiral centers are constrained to be those derived from the synthetic scheme. In the absence of this outside information, the QC predicted ORD, ECD, and VCD for incorrect diastereomers are also found to satisfactorily reproduce the corresponding experimental spectra. Nevertheless, incorrect diastereomers could be eliminated when combined electronic dissymmetry factor (EDF) and vibrational dissymmetry factor (VDF) spectral analyses are included, leaving the correct diastereomer as the sole choice. Thus, the combined EDF and VDF spectral analysis is seen to be a helpful diastereomer discrimination tool. |
format | Online Article Text |
id | pubmed-6648312 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-66483122019-08-27 Dissymmetry Factor Spectral Analysis Can Provide Useful Diastereomer Discrimination: Chiral Molecular Structure of an Analogue of (−)-Crispine A Johnson, Jordan L. Nair, Divya Sadasivan Pillai, Sarath Muraleedharan Johnson, Didimos Kallingathodi, Zabeera Ibnusaud, Ibrahim Polavarapu, Prasad L. ACS Omega [Image: see text] (1R,10bR)-1′-((R)-1,2-Dihydroxyethyl)-1-hydroxy-8,9-dimethoxy1,5,6,10b-tetrahydropyrrolo [2,1-a]isoquinolin-3(2H)-one, an analogue of (−)-crispine A, with three stereogenic centers is synthesized and its absolute configuration (AC) established using the combined information derived from the synthetic scheme and single crystal X-ray diffraction data. The experimental chiroptical spectra (namely, optical rotatory dispersion (ORD), electronic circular dichroism (ECD), and vibrational circular dichroism (VCD)) and the corresponding quantum chemical (QC) predicted spectra for all diastereomers are used to evaluate the AC. The AC of the synthesized compound could be correctly established using any one of the three chiroptical spectroscopic methods (ORD, ECD, or VCD) when the relative configuration is constrained to be that derived from X-ray data or when the ACs of two of the chiral centers are constrained to be those derived from the synthetic scheme. In the absence of this outside information, the QC predicted ORD, ECD, and VCD for incorrect diastereomers are also found to satisfactorily reproduce the corresponding experimental spectra. Nevertheless, incorrect diastereomers could be eliminated when combined electronic dissymmetry factor (EDF) and vibrational dissymmetry factor (VDF) spectral analyses are included, leaving the correct diastereomer as the sole choice. Thus, the combined EDF and VDF spectral analysis is seen to be a helpful diastereomer discrimination tool. American Chemical Society 2019-04-02 /pmc/articles/PMC6648312/ /pubmed/31459760 http://dx.doi.org/10.1021/acsomega.8b03678 Text en Copyright © 2019 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes. |
spellingShingle | Johnson, Jordan L. Nair, Divya Sadasivan Pillai, Sarath Muraleedharan Johnson, Didimos Kallingathodi, Zabeera Ibnusaud, Ibrahim Polavarapu, Prasad L. Dissymmetry Factor Spectral Analysis Can Provide Useful Diastereomer Discrimination: Chiral Molecular Structure of an Analogue of (−)-Crispine A |
title | Dissymmetry Factor Spectral Analysis Can Provide Useful
Diastereomer Discrimination: Chiral Molecular Structure of an Analogue
of (−)-Crispine A |
title_full | Dissymmetry Factor Spectral Analysis Can Provide Useful
Diastereomer Discrimination: Chiral Molecular Structure of an Analogue
of (−)-Crispine A |
title_fullStr | Dissymmetry Factor Spectral Analysis Can Provide Useful
Diastereomer Discrimination: Chiral Molecular Structure of an Analogue
of (−)-Crispine A |
title_full_unstemmed | Dissymmetry Factor Spectral Analysis Can Provide Useful
Diastereomer Discrimination: Chiral Molecular Structure of an Analogue
of (−)-Crispine A |
title_short | Dissymmetry Factor Spectral Analysis Can Provide Useful
Diastereomer Discrimination: Chiral Molecular Structure of an Analogue
of (−)-Crispine A |
title_sort | dissymmetry factor spectral analysis can provide useful
diastereomer discrimination: chiral molecular structure of an analogue
of (−)-crispine a |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6648312/ https://www.ncbi.nlm.nih.gov/pubmed/31459760 http://dx.doi.org/10.1021/acsomega.8b03678 |
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