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Perfluroaryl azides: Reactivities, Unique Reactions and their Applications in the Synthesis of Theranostic Agents
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
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 [en]
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: urn:nbn:se:kth:diva-172950ISBN: 978-91-7595-647-3 (print)OAI: oai:DiVA.org:kth-172950DiVA: diva2:850882
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
List of papers
1. 1,3-Dipolar Cycloaddition Reactivities of Perfluorinated Aryl Azides with Enamines and Strained Dipolarophiles
Open this publication in new window or tab >>1,3-Dipolar Cycloaddition Reactivities of Perfluorinated Aryl Azides with Enamines and Strained Dipolarophiles
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2015 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 137, no 8, 2958-2966 p.Article in journal (Refereed) Published
Abstract [en]

The reactivities of enamines and predistorted (strained) dipolarophiles toward perfluoroaryl azides (PFAAs) were explored experimentally and computationally. Kinetic analyses indicate that PFAAs undergo (3 + 2) cycloadditions with enamines up to 4 orders of magnitude faster than phenyl azide reacts with these dipolarophiles. DFT calculations were used to identify the origin of this rate acceleration. Orbital interactions between the cycloaddends are larger due to the relatively low-lying LUMO of PFAAs. The triazolines resulting from PFAAenamine cycloadditions rearrange to amidines at room temperature, while (3 + 2) cycloadditions of enamines and phenyl azide yield stable, isolable triazolines. The 1,3-dipolar cycloadditions of norbornene and DIBAC also show increased reactivity toward PFAAs over phenyl azide but are slower than enamineazide cycloadditions.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-164457 (URN)10.1021/ja511457g (DOI)000350614700029 ()25553488 (PubMedID)2-s2.0-84924311187 (Scopus ID)
Note

QC 20150423

Available from: 2015-04-23 Created: 2015-04-17 Last updated: 2017-12-04Bibliographically approved
2. Design and synthesis oftheranostic antibiotic nanodrugs that display size-dependent antibacterial activity and luminescence
Open this publication in new window or tab >>Design and synthesis oftheranostic antibiotic nanodrugs that display size-dependent antibacterial activity and luminescence
Show others...
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-172954 (URN)
Note

QS 2015

Available from: 2015-09-03 Created: 2015-09-03 Last updated: 2015-09-03Bibliographically approved
3. Anilide Formation from Thioacids and Perfluoroaryl Azides
Open this publication in new window or tab >>Anilide Formation from Thioacids and Perfluoroaryl Azides
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.

Keyword
Functional groups, Aqueous buffer, Chemical equations, Chemo-selectivity, Fast kinetics, High yield, Metal free, Polar protic, Thioacids
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-169279 (URN)10.1021/acs.joc.5b00240 (DOI)000354004600016 ()25837012 (PubMedID)2-s2.0-84928901913 (Scopus ID)
Note

QC 20150616

Available from: 2015-06-16 Created: 2015-06-12 Last updated: 2017-12-04Bibliographically approved
4. N,N-Diethylurea-Catalyzed Amidation between Electron-Deficient Aryl Azides and Phenylacetaldehydes
Open this publication in new window or tab >>N,N-Diethylurea-Catalyzed Amidation between Electron-Deficient Aryl Azides and Phenylacetaldehydes
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.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-161608 (URN)10.1021/ol503655a (DOI)000349274200062 ()25616121 (PubMedID)2-s2.0-84922590611 (Scopus ID)
Note

QC 20150325

Available from: 2015-03-25 Created: 2015-03-13 Last updated: 2017-12-04Bibliographically approved
5. Base-catalysed synthesis of aryl amides from aryl azides and aldehydes
Open this publication in new window or tab >>Base-catalysed synthesis of aryl amides from aryl azides and aldehydes
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-172953 (URN)
Note

QS 2015

Available from: 2015-09-03 Created: 2015-09-03 Last updated: 2015-09-03Bibliographically approved
6. Photo-activatable switch-on fluorescence through intramolecular C-H insertion of azide derivatives
Open this publication in new window or tab >>Photo-activatable switch-on fluorescence through intramolecular C-H insertion of azide derivatives
(English)Manuscript (preprint) (Other academic)
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-172952 (URN)
Note

QS 2015

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

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