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Substituted nitrogen-bridged diazocines

Novel nitrogen-bridged diazocines (triazocines) were synthesized that carry a formyl or an acetyl group at the CH(2)NR-bridge and bromo- or iodo-substituents at the distant phenyl ring. The photophysical properties were investigated in acetonitrile and water. As compared to previous approaches the y...

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Autores principales: Lentes, Pascal, Rudtke, Jeremy, Griebenow, Thomas, Herges, Rainer
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Beilstein-Institut 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8239257/
https://www.ncbi.nlm.nih.gov/pubmed/34239618
http://dx.doi.org/10.3762/bjoc.17.107
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author Lentes, Pascal
Rudtke, Jeremy
Griebenow, Thomas
Herges, Rainer
author_facet Lentes, Pascal
Rudtke, Jeremy
Griebenow, Thomas
Herges, Rainer
author_sort Lentes, Pascal
collection PubMed
description Novel nitrogen-bridged diazocines (triazocines) were synthesized that carry a formyl or an acetyl group at the CH(2)NR-bridge and bromo- or iodo-substituents at the distant phenyl ring. The photophysical properties were investigated in acetonitrile and water. As compared to previous approaches the yields of the intramolecular azo cyclizations were increased (from ≈40 to 60%) using an oxidative approach starting from the corresponding aniline precursors. The Z→E photoconversion yields in acetonitrile are 80–85% and the thermal half-lives of the metastable E configurations are 31–74 min. Particularly, the high photoconversion yields (≈70%) of the water-soluble diazocines are noteworthy, which makes them promising candidates for applications in photopharmacology. The halogen substituents allow further functionalization via cross-coupling reactions.
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spelling pubmed-82392572021-07-07 Substituted nitrogen-bridged diazocines Lentes, Pascal Rudtke, Jeremy Griebenow, Thomas Herges, Rainer Beilstein J Org Chem Full Research Paper Novel nitrogen-bridged diazocines (triazocines) were synthesized that carry a formyl or an acetyl group at the CH(2)NR-bridge and bromo- or iodo-substituents at the distant phenyl ring. The photophysical properties were investigated in acetonitrile and water. As compared to previous approaches the yields of the intramolecular azo cyclizations were increased (from ≈40 to 60%) using an oxidative approach starting from the corresponding aniline precursors. The Z→E photoconversion yields in acetonitrile are 80–85% and the thermal half-lives of the metastable E configurations are 31–74 min. Particularly, the high photoconversion yields (≈70%) of the water-soluble diazocines are noteworthy, which makes them promising candidates for applications in photopharmacology. The halogen substituents allow further functionalization via cross-coupling reactions. Beilstein-Institut 2021-06-25 /pmc/articles/PMC8239257/ /pubmed/34239618 http://dx.doi.org/10.3762/bjoc.17.107 Text en Copyright © 2021, Lentes et al. https://creativecommons.org/licenses/by/4.0/https://www.beilstein-journals.org/bjoc/terms/termsThis is an Open Access article under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/4.0 (https://creativecommons.org/licenses/by/4.0/) ). Please note that the reuse, redistribution and reproduction in particular requires that the author(s) and source are credited and that individual graphics may be subject to special legal provisions. The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (https://www.beilstein-journals.org/bjoc/terms/terms)
spellingShingle Full Research Paper
Lentes, Pascal
Rudtke, Jeremy
Griebenow, Thomas
Herges, Rainer
Substituted nitrogen-bridged diazocines
title Substituted nitrogen-bridged diazocines
title_full Substituted nitrogen-bridged diazocines
title_fullStr Substituted nitrogen-bridged diazocines
title_full_unstemmed Substituted nitrogen-bridged diazocines
title_short Substituted nitrogen-bridged diazocines
title_sort substituted nitrogen-bridged diazocines
topic Full Research Paper
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8239257/
https://www.ncbi.nlm.nih.gov/pubmed/34239618
http://dx.doi.org/10.3762/bjoc.17.107
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