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A click-based modular approach to introduction of peroxides onto molecules and nanostructures
Copper-promoted azide/alkyne cycloadditions (CuAAC) are explored as a tool for modular introduction of peroxides onto molecules and nanomaterials. Dialkyl peroxide-substituted alkynes undergo Cu(i)-promoted reaction with azides in either organic or biphasic media to furnish peroxide-substituted 1,2,...
Autores principales: | , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9058499/ https://www.ncbi.nlm.nih.gov/pubmed/35517136 http://dx.doi.org/10.1039/d0ra09088c |
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author | Horn, Alissa Dussault, Patrick H. |
author_facet | Horn, Alissa Dussault, Patrick H. |
author_sort | Horn, Alissa |
collection | PubMed |
description | Copper-promoted azide/alkyne cycloadditions (CuAAC) are explored as a tool for modular introduction of peroxides onto molecules and nanomaterials. Dialkyl peroxide-substituted alkynes undergo Cu(i)-promoted reaction with azides in either organic or biphasic media to furnish peroxide-substituted 1,2,3-triazoles. Heterolytic fragmentation of the peroxide to an aldehyde, a side reaction that appears to be related to the formation of the triazole, can be suppressed by use of excess alkyne, the presence of triethylsilane, or by use of iodoalkyne substrates. Complementary reactions of simple alkynes with azido-substituted peroxides are much less efficient. Click reactions of alkynyl peroxyacetals are also reported; reductive fragmentation can be minimized by increasing the distance between the peroxyacetal and the alkyne. The strategy enables modular introduction of dialkyl peroxides and peroxyacetals onto gold nanoparticles, the first such process to be reported. |
format | Online Article Text |
id | pubmed-9058499 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-90584992022-05-04 A click-based modular approach to introduction of peroxides onto molecules and nanostructures Horn, Alissa Dussault, Patrick H. RSC Adv Chemistry Copper-promoted azide/alkyne cycloadditions (CuAAC) are explored as a tool for modular introduction of peroxides onto molecules and nanomaterials. Dialkyl peroxide-substituted alkynes undergo Cu(i)-promoted reaction with azides in either organic or biphasic media to furnish peroxide-substituted 1,2,3-triazoles. Heterolytic fragmentation of the peroxide to an aldehyde, a side reaction that appears to be related to the formation of the triazole, can be suppressed by use of excess alkyne, the presence of triethylsilane, or by use of iodoalkyne substrates. Complementary reactions of simple alkynes with azido-substituted peroxides are much less efficient. Click reactions of alkynyl peroxyacetals are also reported; reductive fragmentation can be minimized by increasing the distance between the peroxyacetal and the alkyne. The strategy enables modular introduction of dialkyl peroxides and peroxyacetals onto gold nanoparticles, the first such process to be reported. The Royal Society of Chemistry 2020-12-16 /pmc/articles/PMC9058499/ /pubmed/35517136 http://dx.doi.org/10.1039/d0ra09088c Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/ |
spellingShingle | Chemistry Horn, Alissa Dussault, Patrick H. A click-based modular approach to introduction of peroxides onto molecules and nanostructures |
title | A click-based modular approach to introduction of peroxides onto molecules and nanostructures |
title_full | A click-based modular approach to introduction of peroxides onto molecules and nanostructures |
title_fullStr | A click-based modular approach to introduction of peroxides onto molecules and nanostructures |
title_full_unstemmed | A click-based modular approach to introduction of peroxides onto molecules and nanostructures |
title_short | A click-based modular approach to introduction of peroxides onto molecules and nanostructures |
title_sort | click-based modular approach to introduction of peroxides onto molecules and nanostructures |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9058499/ https://www.ncbi.nlm.nih.gov/pubmed/35517136 http://dx.doi.org/10.1039/d0ra09088c |
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