Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Anilide Formation from Thioacids and Perfluoroaryl Azides
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry. University of Massachusetts, United States.ORCID iD: 0000-0003-1121-4007
2015 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 80, no 9, 4392-4397 p.Article in journal (Refereed) Published
Abstract [en]

A metal-free method for fast and clean anilide formation from perfluoroaryl azide and thioacid is presented. The reaction proved highly efficient, displaying fast kinetics, high yield, and good chemoselectivity. The transformation was compatible with various solvents and tolerant to a wide variety of functional groups, and it showed high performance in polar protic/aprotic media, including aqueous buffer systems.

Place, publisher, year, edition, pages
2015. Vol. 80, no 9, 4392-4397 p.
Keyword [en]
Functional groups, Aqueous buffer, Chemical equations, Chemo-selectivity, Fast kinetics, High yield, Metal free, Polar protic, Thioacids
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-169279DOI: 10.1021/acs.joc.5b00240ISI: 000354004600016PubMedID: 25837012Scopus ID: 2-s2.0-84928901913OAI: oai:DiVA.org:kth-169279DiVA: diva2:822364
Note

QC 20150616

Available from: 2015-06-16 Created: 2015-06-12 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

Open Access in DiVA

No full text

Other links

Publisher's full textPubMedScopus

Search in DiVA

By author/editor
Xie, ShengFukumoto, RyoRamström, OlofYan, Mingdi
By organisation
Organic Chemistry
In the same journal
Journal of Organic Chemistry
Organic Chemistry

Search outside of DiVA

GoogleGoogle Scholar

doi
pubmed
urn-nbn

Altmetric score

doi
pubmed
urn-nbn
Total: 32 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf