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An ingenious method for the determination of the relative and absolute configurations of compounds containing aryl-glycerol fragments by (1)H NMR spectroscopy
A concise method was established to determine the relative and absolute configurations of aryl-glycerols that depend on the chemical shift differences (Δδ) of the diastereotopic methylene protons (H-3) by (1)H NMR spectroscopy. When using DMSO-d(6) as the preferred solvent, the threo configuration c...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8695069/ https://www.ncbi.nlm.nih.gov/pubmed/35423312 http://dx.doi.org/10.1039/d0ra09712h |
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author | Zhang, Xu Lu, Kai-Zhou Yan, Hai-Wei Feng, Zi-Ming Yang, Ya-Nan Jiang, Jian-Shuang Zhang, Pei-Cheng |
author_facet | Zhang, Xu Lu, Kai-Zhou Yan, Hai-Wei Feng, Zi-Ming Yang, Ya-Nan Jiang, Jian-Shuang Zhang, Pei-Cheng |
author_sort | Zhang, Xu |
collection | PubMed |
description | A concise method was established to determine the relative and absolute configurations of aryl-glycerols that depend on the chemical shift differences (Δδ) of the diastereotopic methylene protons (H-3) by (1)H NMR spectroscopy. When using DMSO-d(6) as the preferred solvent, the threo configuration corresponded to a larger Δδ(H3a–H3b) value (>0.15 ppm), whereas the erythro configuration (<0.07 ppm) corresponded to a smaller value. Furthermore, the absolute configurations were determined with the aid of a simple acylation reaction through camphanoyl chloride. In the threo enantiomers, the Δδ value of the 1R,2R configuration was <0.15 ppm, and that of the 1S,2S configuration was >0.20 ppm. In the erythro enantiomers, the Δδ value of 1R,2S was >0.09 ppm, and that of 1S,2R was <0.05 ppm. Remarkably, this empirical rule is invalid in CDCl(3). In addition, this method was also verified by a quantum (1)H NMR calculation. |
format | Online Article Text |
id | pubmed-8695069 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-86950692022-04-13 An ingenious method for the determination of the relative and absolute configurations of compounds containing aryl-glycerol fragments by (1)H NMR spectroscopy Zhang, Xu Lu, Kai-Zhou Yan, Hai-Wei Feng, Zi-Ming Yang, Ya-Nan Jiang, Jian-Shuang Zhang, Pei-Cheng RSC Adv Chemistry A concise method was established to determine the relative and absolute configurations of aryl-glycerols that depend on the chemical shift differences (Δδ) of the diastereotopic methylene protons (H-3) by (1)H NMR spectroscopy. When using DMSO-d(6) as the preferred solvent, the threo configuration corresponded to a larger Δδ(H3a–H3b) value (>0.15 ppm), whereas the erythro configuration (<0.07 ppm) corresponded to a smaller value. Furthermore, the absolute configurations were determined with the aid of a simple acylation reaction through camphanoyl chloride. In the threo enantiomers, the Δδ value of the 1R,2R configuration was <0.15 ppm, and that of the 1S,2S configuration was >0.20 ppm. In the erythro enantiomers, the Δδ value of 1R,2S was >0.09 ppm, and that of 1S,2R was <0.05 ppm. Remarkably, this empirical rule is invalid in CDCl(3). In addition, this method was also verified by a quantum (1)H NMR calculation. The Royal Society of Chemistry 2021-02-19 /pmc/articles/PMC8695069/ /pubmed/35423312 http://dx.doi.org/10.1039/d0ra09712h Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/ |
spellingShingle | Chemistry Zhang, Xu Lu, Kai-Zhou Yan, Hai-Wei Feng, Zi-Ming Yang, Ya-Nan Jiang, Jian-Shuang Zhang, Pei-Cheng An ingenious method for the determination of the relative and absolute configurations of compounds containing aryl-glycerol fragments by (1)H NMR spectroscopy |
title | An ingenious method for the determination of the relative and absolute configurations of compounds containing aryl-glycerol fragments by (1)H NMR spectroscopy |
title_full | An ingenious method for the determination of the relative and absolute configurations of compounds containing aryl-glycerol fragments by (1)H NMR spectroscopy |
title_fullStr | An ingenious method for the determination of the relative and absolute configurations of compounds containing aryl-glycerol fragments by (1)H NMR spectroscopy |
title_full_unstemmed | An ingenious method for the determination of the relative and absolute configurations of compounds containing aryl-glycerol fragments by (1)H NMR spectroscopy |
title_short | An ingenious method for the determination of the relative and absolute configurations of compounds containing aryl-glycerol fragments by (1)H NMR spectroscopy |
title_sort | ingenious method for the determination of the relative and absolute configurations of compounds containing aryl-glycerol fragments by (1)h nmr spectroscopy |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8695069/ https://www.ncbi.nlm.nih.gov/pubmed/35423312 http://dx.doi.org/10.1039/d0ra09712h |
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