Perfluroaryl azides: Reactivities, Unique Reactions and their Applications in the Synthesis of Theranostic Agents
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
The work centersaround perfluoroaryl azides (PFAAs), and theirability to undergo certain fast and robusttransformations. The chemistry was furtherappliedfor biomedical applications.
The first section focuses on the azide-aldehyde-amine cycloaddition using PFAAs. Experimental and computational investigations uncovered a fast azide-enamine cycloaddition to form triazolines, which spontaneously rearrange into stable amidine products. In addition, this transformation was explored in the formulation of pure nanodrugs. Because this reaction can introduce a phenyl and a perfluoroaryl moiety enabling supramolecular interactions near the antibiotic drug, the resulting ciprofloxacin derivatives formed nano-sized aggregates by precipitation, which displayed aggregation-induced emission for bacterial imaging as well as enhanced size-dependent antibacterial efficacy.
In the second section, the high electrophilicity of PFAAs was explored to transform azides to aryl amides. The reactivity of PFAAs in the thioacid/azide reaction was studied. In addition, PFAAs were discovered to react with phenylacetaldehyde to form aryl amidesviaan azide-enol cycloaddition, similar tothe perfluoroaryl azide-aldehyde-amine reaction.This strategyof amide synthesiswas furthermoregeneralized through a combination of base-catalyzed azide-enolate cycloaddition reaction and acid-or heat-promoted rearrangement of triazolines.
The last section describes a type of azide fluorogens whose fluorescence can be switched on by alight-initiated intramolecular nitrene insertion intoa C-H bond in the neighboring aromaticring. These fluorogenic structures were efficiently accessed via the direct nucleophilic aromatic substitution of PFAAs.
Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2015. , 68 p.
TRITA-CHE-Report, ISSN 1654-1081 ; 2015:37
Click Chemistry, Dipolar Cycloaddition, Enamine, Triazoline, Amidine, Aggregation-induced emission, pure nanodrugs, aryl amide, thioacid/azide reaction, nucleophilic aromatic substitution, azide-masked fluorophore, nitrene insertion
Engineering and Technology Natural Sciences
Research subject Chemistry
IdentifiersURN: urn:nbn:se:kth:diva-172950ISBN: 978-91-7595-647-3OAI: oai:DiVA.org:kth-172950DiVA: diva2:850882
2015-09-25, F3, Lindstedtsvägen 26, KTH, Stockholm, 14:00 (English)
Bräse, Stefan, Professor
Yan, Mingdi, ProfessorRamström, Olof, Professor
QC 201509032015-09-032015-09-022015-09-03Bibliographically approved
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