Cargando…
Evaluating the Effectiveness of Tethered Bis(urazolyl) Diradicals as Molecular Building Blocks for Dynamic Covalent Chemistry
[Image: see text] Dynamic covalent chemistry (DCvC) is a powerful means by which to rapidly prepare complex structures from simple molecular building blocks. Effective DCvC behavior is contingent upon the reversibility of covalent bond formation. Stabilized radical species, therefore, have been effe...
Autores principales: | , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
|
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10337031/ https://www.ncbi.nlm.nih.gov/pubmed/37364258 http://dx.doi.org/10.1021/acs.joc.3c00732 |
_version_ | 1785071329315127296 |
---|---|
author | Breton, Gary W. Martin, Kenneth L. Bowron, James Alexander Bacsa, John |
author_facet | Breton, Gary W. Martin, Kenneth L. Bowron, James Alexander Bacsa, John |
author_sort | Breton, Gary W. |
collection | PubMed |
description | [Image: see text] Dynamic covalent chemistry (DCvC) is a powerful means by which to rapidly prepare complex structures from simple molecular building blocks. Effective DCvC behavior is contingent upon the reversibility of covalent bond formation. Stabilized radical species, therefore, have been effectively used for these applications. In earlier work we demonstrated that properly substituted 1-arylurazolyl radicals showed promise as oxygen-insensitive heterocyclic N-centered radicals with a propensity for reversible bond formation. In this work we have synthesized several tethered bis(urazolyl) diradicals, varying by the type and length of connectivity between the urazole rings, and tested them for DCvC behavior. We have found that when the two aryl rings to which the urazolyl radical sites are attached are tethered by a chain of five or more carbons, equilibrium mixtures of monomeric and dimeric species are formed by N–N bond formation between two radical sites. DCvC behavior is observed that is sensitive to changes in temperature, concentration, and (to a lesser extent) solvent. In general, the dimer species is favored at lower temperatures and higher concentrations. |
format | Online Article Text |
id | pubmed-10337031 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-103370312023-07-13 Evaluating the Effectiveness of Tethered Bis(urazolyl) Diradicals as Molecular Building Blocks for Dynamic Covalent Chemistry Breton, Gary W. Martin, Kenneth L. Bowron, James Alexander Bacsa, John J Org Chem [Image: see text] Dynamic covalent chemistry (DCvC) is a powerful means by which to rapidly prepare complex structures from simple molecular building blocks. Effective DCvC behavior is contingent upon the reversibility of covalent bond formation. Stabilized radical species, therefore, have been effectively used for these applications. In earlier work we demonstrated that properly substituted 1-arylurazolyl radicals showed promise as oxygen-insensitive heterocyclic N-centered radicals with a propensity for reversible bond formation. In this work we have synthesized several tethered bis(urazolyl) diradicals, varying by the type and length of connectivity between the urazole rings, and tested them for DCvC behavior. We have found that when the two aryl rings to which the urazolyl radical sites are attached are tethered by a chain of five or more carbons, equilibrium mixtures of monomeric and dimeric species are formed by N–N bond formation between two radical sites. DCvC behavior is observed that is sensitive to changes in temperature, concentration, and (to a lesser extent) solvent. In general, the dimer species is favored at lower temperatures and higher concentrations. American Chemical Society 2023-06-26 /pmc/articles/PMC10337031/ /pubmed/37364258 http://dx.doi.org/10.1021/acs.joc.3c00732 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Breton, Gary W. Martin, Kenneth L. Bowron, James Alexander Bacsa, John Evaluating the Effectiveness of Tethered Bis(urazolyl) Diradicals as Molecular Building Blocks for Dynamic Covalent Chemistry |
title | Evaluating the Effectiveness
of Tethered Bis(urazolyl)
Diradicals as Molecular Building Blocks for Dynamic Covalent Chemistry |
title_full | Evaluating the Effectiveness
of Tethered Bis(urazolyl)
Diradicals as Molecular Building Blocks for Dynamic Covalent Chemistry |
title_fullStr | Evaluating the Effectiveness
of Tethered Bis(urazolyl)
Diradicals as Molecular Building Blocks for Dynamic Covalent Chemistry |
title_full_unstemmed | Evaluating the Effectiveness
of Tethered Bis(urazolyl)
Diradicals as Molecular Building Blocks for Dynamic Covalent Chemistry |
title_short | Evaluating the Effectiveness
of Tethered Bis(urazolyl)
Diradicals as Molecular Building Blocks for Dynamic Covalent Chemistry |
title_sort | evaluating the effectiveness
of tethered bis(urazolyl)
diradicals as molecular building blocks for dynamic covalent chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10337031/ https://www.ncbi.nlm.nih.gov/pubmed/37364258 http://dx.doi.org/10.1021/acs.joc.3c00732 |
work_keys_str_mv | AT bretongaryw evaluatingtheeffectivenessoftetheredbisurazolyldiradicalsasmolecularbuildingblocksfordynamiccovalentchemistry AT martinkennethl evaluatingtheeffectivenessoftetheredbisurazolyldiradicalsasmolecularbuildingblocksfordynamiccovalentchemistry AT bowronjamesalexander evaluatingtheeffectivenessoftetheredbisurazolyldiradicalsasmolecularbuildingblocksfordynamiccovalentchemistry AT bacsajohn evaluatingtheeffectivenessoftetheredbisurazolyldiradicalsasmolecularbuildingblocksfordynamiccovalentchemistry |