The Phenomenon of Self-Induced Diastereomeric Anisochrony and Its Implications in NMR Spectroscopy
Nuclear magnetic resonance (NMR) spectroscopy is an analytical technique largely applied in the analysis of discrimination processes involving enantiomeric substrates and chiral agents, which can interact with the analyte either via covalent bonding or via formation of diastereomeric solvates. Howev...
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| Format: | Article |
| Language: | English |
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MDPI AG
2023-09-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/19/6854 |
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| author | Federica Aiello Gloria Uccello Barretta Federica Balzano Fabio Spiaggia |
| author_facet | Federica Aiello Gloria Uccello Barretta Federica Balzano Fabio Spiaggia |
| author_sort | Federica Aiello |
| collection | DOAJ |
| description | Nuclear magnetic resonance (NMR) spectroscopy is an analytical technique largely applied in the analysis of discrimination processes involving enantiomeric substrates and chiral agents, which can interact with the analyte either via covalent bonding or via formation of diastereomeric solvates. However, enantiodiscrimination has been observed, in some cases, even in the absence of any additional chiral selector. The reasons behind this phenomenon must be found in the capability of some chiral substrates to interact with themselves by forming diastereomeric solvates in solution that can generate nonequivalences in the NMR spectra of enantiomerically enriched mixtures. As a result, differentiation of enantiomers is observed, thus allowing the quantification of the enantiomeric composition of the mixture under investigation. The tendency of certain substrates to self-aggregate and to generate diastereomeric adducts in solution can be defined as Self-Induced Diastereomeric Anisochrony (SIDA), but other acronyms have been used to refer to this phenomenon. In the present work, an overview of SIDA processes investigated via NMR spectroscopy will be provided, with a particular emphasis on the nature of the substrates involved, on the interaction mechanisms at the basis of the phenomenon, and on theoretical treatments proposed in the literature to explain them. |
| first_indexed | 2024-03-10T21:40:18Z |
| format | Article |
| id | doaj.art-f242375a43f74bcb944bca0832807034 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T21:40:18Z |
| publishDate | 2023-09-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-f242375a43f74bcb944bca08328070342023-11-19T14:46:29ZengMDPI AGMolecules1420-30492023-09-012819685410.3390/molecules28196854The Phenomenon of Self-Induced Diastereomeric Anisochrony and Its Implications in NMR SpectroscopyFederica Aiello0Gloria Uccello Barretta1Federica Balzano2Fabio Spiaggia3National Research Council, Institute for Chemical and Physical Processes (CNR-IPCF), Via G. Moruzzi 1, 56124 Pisa, ItalyDepartment of Chemistry and Industrial Chemistry, University of Pisa, Via G. Moruzzi 13, 56124 Pisa, ItalyDepartment of Chemistry and Industrial Chemistry, University of Pisa, Via G. Moruzzi 13, 56124 Pisa, ItalyDepartment of Chemistry and Industrial Chemistry, University of Pisa, Via G. Moruzzi 13, 56124 Pisa, ItalyNuclear magnetic resonance (NMR) spectroscopy is an analytical technique largely applied in the analysis of discrimination processes involving enantiomeric substrates and chiral agents, which can interact with the analyte either via covalent bonding or via formation of diastereomeric solvates. However, enantiodiscrimination has been observed, in some cases, even in the absence of any additional chiral selector. The reasons behind this phenomenon must be found in the capability of some chiral substrates to interact with themselves by forming diastereomeric solvates in solution that can generate nonequivalences in the NMR spectra of enantiomerically enriched mixtures. As a result, differentiation of enantiomers is observed, thus allowing the quantification of the enantiomeric composition of the mixture under investigation. The tendency of certain substrates to self-aggregate and to generate diastereomeric adducts in solution can be defined as Self-Induced Diastereomeric Anisochrony (SIDA), but other acronyms have been used to refer to this phenomenon. In the present work, an overview of SIDA processes investigated via NMR spectroscopy will be provided, with a particular emphasis on the nature of the substrates involved, on the interaction mechanisms at the basis of the phenomenon, and on theoretical treatments proposed in the literature to explain them.https://www.mdpi.com/1420-3049/28/19/6854self-aggregationhomodimersheterodimersnonequivalencedimerization constantenantiomers |
| spellingShingle | Federica Aiello Gloria Uccello Barretta Federica Balzano Fabio Spiaggia The Phenomenon of Self-Induced Diastereomeric Anisochrony and Its Implications in NMR Spectroscopy Molecules self-aggregation homodimers heterodimers nonequivalence dimerization constant enantiomers |
| title | The Phenomenon of Self-Induced Diastereomeric Anisochrony and Its Implications in NMR Spectroscopy |
| title_full | The Phenomenon of Self-Induced Diastereomeric Anisochrony and Its Implications in NMR Spectroscopy |
| title_fullStr | The Phenomenon of Self-Induced Diastereomeric Anisochrony and Its Implications in NMR Spectroscopy |
| title_full_unstemmed | The Phenomenon of Self-Induced Diastereomeric Anisochrony and Its Implications in NMR Spectroscopy |
| title_short | The Phenomenon of Self-Induced Diastereomeric Anisochrony and Its Implications in NMR Spectroscopy |
| title_sort | phenomenon of self induced diastereomeric anisochrony and its implications in nmr spectroscopy |
| topic | self-aggregation homodimers heterodimers nonequivalence dimerization constant enantiomers |
| url | https://www.mdpi.com/1420-3049/28/19/6854 |
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