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Neutral Chiral Tetrakis‐Iodo‐Triazole Halogen‐Bond Donor for Chiral Recognition and Enantioselective Catalysis
Halogen bonding represents a powerful tool in the field of noncovalent interactions. However, applications in enantioselective recognition and catalysis remain almost nonexistent, due in part to the distinct features of halogen bonds, including long covalent and noncovalent bond distances and high d...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7898328/ https://www.ncbi.nlm.nih.gov/pubmed/33210767 http://dx.doi.org/10.1002/chem.202005016 |
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author | Ostler, Florian Piekarski, Dariusz G. Danelzik, Tobias Taylor, Mark S. García Mancheño, Olga |
author_facet | Ostler, Florian Piekarski, Dariusz G. Danelzik, Tobias Taylor, Mark S. García Mancheño, Olga |
author_sort | Ostler, Florian |
collection | PubMed |
description | Halogen bonding represents a powerful tool in the field of noncovalent interactions. However, applications in enantioselective recognition and catalysis remain almost nonexistent, due in part to the distinct features of halogen bonds, including long covalent and noncovalent bond distances and high directionality. Herein, this work presents a novel chiral tetrakis‐iodo‐triazole structure as a neutral halogen bond donor for both chiral anion‐recognition and enantioinduction in ion‐pair organocatalysis. NMR‐titration studies revealed significant differences in anion affinity between the halogen bonding receptor and its hydrogen bonding parent. Selective recognition of chiral dicarboxylates and asymmetric induction in a benchmark organocatalytic reaction were demonstrated using the halogen bond donor. Inversions in the absolute sense of chiral recognition, enantioselectivity, and chiroptical properties relative to the related hydrogen donor were observed. Computational modeling suggested that these effects were the result of distinct anion‐binding modes for the halogen‐ versus hydrogen‐bond donors. |
format | Online Article Text |
id | pubmed-7898328 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-78983282021-03-03 Neutral Chiral Tetrakis‐Iodo‐Triazole Halogen‐Bond Donor for Chiral Recognition and Enantioselective Catalysis Ostler, Florian Piekarski, Dariusz G. Danelzik, Tobias Taylor, Mark S. García Mancheño, Olga Chemistry Communications Halogen bonding represents a powerful tool in the field of noncovalent interactions. However, applications in enantioselective recognition and catalysis remain almost nonexistent, due in part to the distinct features of halogen bonds, including long covalent and noncovalent bond distances and high directionality. Herein, this work presents a novel chiral tetrakis‐iodo‐triazole structure as a neutral halogen bond donor for both chiral anion‐recognition and enantioinduction in ion‐pair organocatalysis. NMR‐titration studies revealed significant differences in anion affinity between the halogen bonding receptor and its hydrogen bonding parent. Selective recognition of chiral dicarboxylates and asymmetric induction in a benchmark organocatalytic reaction were demonstrated using the halogen bond donor. Inversions in the absolute sense of chiral recognition, enantioselectivity, and chiroptical properties relative to the related hydrogen donor were observed. Computational modeling suggested that these effects were the result of distinct anion‐binding modes for the halogen‐ versus hydrogen‐bond donors. John Wiley and Sons Inc. 2021-01-07 2021-02-01 /pmc/articles/PMC7898328/ /pubmed/33210767 http://dx.doi.org/10.1002/chem.202005016 Text en © 2020 The Authors. Published by Wiley-VCH GmbH This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made. |
spellingShingle | Communications Ostler, Florian Piekarski, Dariusz G. Danelzik, Tobias Taylor, Mark S. García Mancheño, Olga Neutral Chiral Tetrakis‐Iodo‐Triazole Halogen‐Bond Donor for Chiral Recognition and Enantioselective Catalysis |
title | Neutral Chiral Tetrakis‐Iodo‐Triazole Halogen‐Bond Donor for Chiral Recognition and Enantioselective Catalysis |
title_full | Neutral Chiral Tetrakis‐Iodo‐Triazole Halogen‐Bond Donor for Chiral Recognition and Enantioselective Catalysis |
title_fullStr | Neutral Chiral Tetrakis‐Iodo‐Triazole Halogen‐Bond Donor for Chiral Recognition and Enantioselective Catalysis |
title_full_unstemmed | Neutral Chiral Tetrakis‐Iodo‐Triazole Halogen‐Bond Donor for Chiral Recognition and Enantioselective Catalysis |
title_short | Neutral Chiral Tetrakis‐Iodo‐Triazole Halogen‐Bond Donor for Chiral Recognition and Enantioselective Catalysis |
title_sort | neutral chiral tetrakis‐iodo‐triazole halogen‐bond donor for chiral recognition and enantioselective catalysis |
topic | Communications |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7898328/ https://www.ncbi.nlm.nih.gov/pubmed/33210767 http://dx.doi.org/10.1002/chem.202005016 |
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