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N,N-Diethylurea-Catalyzed Amidation between Electron-Deficient Aryl Azides and Phenylacetaldehydes
KTH, School of Chemical Science and Engineering (CHE), Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry. University of Massachusetts Lowell, United States.ORCID iD: 0000-0003-1121-4007
2015 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 17, no 3, 636-639 p.Article in journal (Refereed) Published
Abstract [en]

Urea structures, of which N,N-diethylurea (DEU) proved to be the most efficient, were discovered to catalyze amidation reactions between electron-deficient aryl azides and phenylacetaldehydes. Experimental data support 1,3-dipolar cycloaddition between DEU-activated enols and electrophilic phenyl azides, especially perfluoroaryl azides, followed by rearrangement of the triazoline intermediate. The activation of the aldehyde under near-neutral conditions was of special importance in inhibiting dehydration/aromatization of the triazoline intermediate, thus promoting the rearrangement to form aryl amides.

Place, publisher, year, edition, pages
2015. Vol. 17, no 3, 636-639 p.
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-161608DOI: 10.1021/ol503655aISI: 000349274200062PubMedID: 25616121Scopus ID: 2-s2.0-84922590611OAI: oai:DiVA.org:kth-161608DiVA: diva2:797946
Note

QC 20150325

Available from: 2015-03-25 Created: 2015-03-13 Last updated: 2017-12-04Bibliographically approved
In thesis
1. Perfluroaryl azides: Reactivities, Unique Reactions and their Applications in the Synthesis of Theranostic Agents
Open this publication in new window or tab >>Perfluroaryl azides: Reactivities, Unique Reactions and their Applications in the Synthesis of Theranostic Agents
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

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.
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2015:37
Keyword
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
National Category
Engineering and Technology Natural Sciences
Research subject
Chemistry
Identifiers
urn:nbn:se:kth:diva-172950 (URN)978-91-7595-647-3 (ISBN)
Public defence
2015-09-25, F3, Lindstedtsvägen 26, KTH, Stockholm, 14:00 (English)
Opponent
Supervisors
Note

QC 20150903

Available from: 2015-09-03 Created: 2015-09-02 Last updated: 2015-09-03Bibliographically approved

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