Developing Photoactive Coumarin-Caged N-Hydroxysulfonamides for Generation of Nitroxyl (HNO)

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aut.relation.issue16
aut.relation.journalMolecules
aut.relation.startpage3918
aut.relation.volume29
dc.contributor.authorRahman, MS
dc.contributor.authorBharadwaj, V
dc.contributor.authorLautaha, AKHS
dc.contributor.authorSampson, P
dc.contributor.authorBrasch, NE
dc.contributor.authorSeed, AJ
dc.date.accessioned2024-11-06T00:10:22Z
dc.date.available2024-11-06T00:10:22Z
dc.date.issued2024-08-19
dc.description.abstractPhotoactive N-hydroxysulfonamides photocaged with the (6-bromo-7-hydroxycoumarin-4-yl)methyl chromophore have been successfully synthesized, and the mechanisms of photodecomposition investigated for two of the compounds. Upon irradiation up to 97% of a diagnostic marker for (H)NO release, sulfinate was observed for the trifluoromethanesulfonamide system. In the absence of a species that reacts rapidly with (H)NO, (H)NO instead reacts with the carbocation intermediate to ultimately generate (E)-BHC-oxime and (Z)-BHC-oxime. Alternatively, the carbocation intermediate reacts with solvent water to give a diol. Deprotonation of the N(H) proton is required for HNO generation via concerted C-O/N-S bond cleavage, whereas the protonation state of the O(H) does not affect the observed photoproducts. If the N(H) is protonated, C-O bond cleavage to generate the parent N-hydroxysulfonamide will occur, and/or O-N bond cleavage to generate a sulfonamide. The undesired competing O-N bond cleavage pathway increases when the volume percentage of water in acetonitrile/water solvent mixtures is increased.
dc.identifier.citationMolecules, ISSN: 1420-3049 (Print); 1420-3049 (Online), MDPI AG, 29(16), 3918-. doi: 10.3390/molecules29163918
dc.identifier.doi10.3390/molecules29163918
dc.identifier.issn1420-3049
dc.identifier.issn1420-3049
dc.identifier.urihttp://hdl.handle.net/10292/18232
dc.languageeng
dc.publisherMDPI AG
dc.relation.urihttps://www.mdpi.com/1420-3049/29/16/3918
dc.rights© 2024 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
dc.rights.accessrightsOpenAccess
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/
dc.subjectHNO
dc.subjectN-hydroxysulfonamide
dc.subjectPiloty’s acid
dc.subjectnitroxyl
dc.subjectphotocage
dc.subjectphotochemistry
dc.subject3402 Inorganic Chemistry
dc.subject34 Chemical Sciences
dc.subject0304 Medicinal and Biomolecular Chemistry
dc.subject0305 Organic Chemistry
dc.subject0307 Theoretical and Computational Chemistry
dc.subjectOrganic Chemistry
dc.subject3404 Medicinal and biomolecular chemistry
dc.subject3405 Organic chemistry
dc.titleDeveloping Photoactive Coumarin-Caged N-Hydroxysulfonamides for Generation of Nitroxyl (HNO)
dc.typeJournal Article
pubs.elements-id568533
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