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Special Issue "Organic Azides"

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organic Synthesis".

Deadline for manuscript submissions: closed (30 October 2015)

Special Issue Editor

Guest Editor
Prof. Dr. Klaus Banert

Chemnitz University of Technology, Organic Chemistry, Strasse der Nationen 62, 09111 Chemnitz, Germany
Website | E-Mail
Interests: synthetic methods; reaction mechanisms; short-lived species; structure assignments; organic azides; heterocycles; cycloaddition reactions

Special Issue Information

Dear Colleagues,

The azido unit in organic molecules is not only a highly useful device to synthesize a variety of nitrogen-containing products, such as amines and amine derivatives, several types of heterocycles, nitrene-derived compounds, and many others, it also represents one of the most fascinating and stimulating functional groups. After the discovery of aryl azides as the first organic azides (P. Griess, 1864), the further development of azides chemistry was only more or less continuous in the last 150 years. A large number of applications in organic synthesis as well as material sciences and life sciences underline the importance of organic azides since the 1960s.

In the last decade, however, the development of azide chemistry has become very rapid owing to the introduction of copper-catalyzed cycloaddition of azides at terminal alkynes (M. Meldal, K. B. Sharpless, 2002, click chemistry) and also because of several other new reactions such as oxidation and radical reactions with organic azides. Furthermore, molecules with novel combinations of the azido unit and adjacent other functional groups, as well as new applications of organic azides as high-energy materials and in biochemically relevant ligation and labeling methods have increased the general interest in azido compounds.

In this Special Issue of Molecules, research articles covering all areas of organic azide chemistry are welcome to present the latest state of research in connection with this exciting functional group.

Klaus Banert
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1800 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • –  synthesis of organic azides
  • –  new types of organic azides
  • –  novel reactions of organic azides
  • –  application in bioorganic chemistry
  • –  application in material sciences

Published Papers (8 papers)

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Research

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Open AccessFeature PaperArticle Porphyrin Cobalt(III) “Nitrene Radical” Reactivity; Hydrogen Atom Transfer from Ortho-YH Substituents to the Nitrene Moiety of Cobalt-Bound Aryl Nitrene Intermediates (Y = O, NH)
Molecules 2016, 21(2), 242; doi:10.3390/molecules21020242
Received: 16 January 2016 / Revised: 5 February 2016 / Accepted: 16 February 2016 / Published: 20 February 2016
Cited by 3 | PDF Full-text (5674 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
In the field of cobalt(II) porphyrin-catalyzed metallo-radical reactions, organic azides have emerged as successful nitrene transfer reagents. In the pursuit of employing ortho-YH substituted (Y = O, NH) aryl azides in Co(II) porphyrin-catalyzed nitrene transfer reactions, unexpected hydrogen atom transfer (HAT) from
[...] Read more.
In the field of cobalt(II) porphyrin-catalyzed metallo-radical reactions, organic azides have emerged as successful nitrene transfer reagents. In the pursuit of employing ortho-YH substituted (Y = O, NH) aryl azides in Co(II) porphyrin-catalyzed nitrene transfer reactions, unexpected hydrogen atom transfer (HAT) from the OH or NH2 group in the ortho-position to the nitrene moiety of the key radical-intermediate was observed. This leads to formation of reactive ortho-iminoquinonoid (Y = O) and phenylene diimine (Y = NH) species. These intermediates convert to subsequent products in non-catalyzed reactions, as is typical for these free organic compounds. As such, the observed reactions prevent the anticipated cobalt-mediated catalytic radical-type coupling of the nitrene radical intermediates to alkynes or alkenes. Nonetheless, the observed reactions provide valuable insights into the reactivity of transition metal nitrene-radical intermediates, and give access to ortho-iminoquinonoid and phenylene diimine intermediates from ortho-YH substituted aryl azides in a catalytic manner. The latter can be employed as intermediates in one-pot catalytic transformations. From the ortho-hydroxy aryl azide substrates both phenoxizinones and benzoxazines could be synthesized in high yields. From the ortho-amino aryl azide substrates azabenzene compounds were obtained as the main products. Computational studies support these observations, and reveal that HAT from the neighboring OH and NH2 moiety to the nitrene radical moiety has a low energy barrier. Full article
(This article belongs to the Special Issue Organic Azides)
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Open AccessArticle Improved Schmidt Conversion of Aldehydes to Nitriles Using Azidotrimethylsilane in 1,1,1,3,3,3-Hexafluoro-2-propanol
Molecules 2016, 21(1), 45; doi:10.3390/molecules21010045
Received: 5 November 2015 / Revised: 16 December 2015 / Accepted: 22 December 2015 / Published: 29 December 2015
Cited by 3 | PDF Full-text (16507 KB) | HTML Full-text | XML Full-text
Abstract
The Schmidt reaction of aromatic aldehydes using a substoichiometric amount (40 mol %) of triflic acid is described. Low catalyst loading was enabled by a strong hydrogen-bond-donating solvent hexafluoro-2-propanol (HFIP). This improved protocol tolerates a broad scope of aldehydes with diverse functional groups
[...] Read more.
The Schmidt reaction of aromatic aldehydes using a substoichiometric amount (40 mol %) of triflic acid is described. Low catalyst loading was enabled by a strong hydrogen-bond-donating solvent hexafluoro-2-propanol (HFIP). This improved protocol tolerates a broad scope of aldehydes with diverse functional groups and the corresponding nitriles were obtained in good to high yields without the need for aqueous work up. Full article
(This article belongs to the Special Issue Organic Azides)
Open AccessArticle Synthesis of New 2-Halo-2-(1H-tetrazol-5-yl)-2H-azirines via a Non-Classical Wittig Reaction
Molecules 2015, 20(12), 22351-22363; doi:10.3390/molecules201219848
Received: 30 October 2015 / Revised: 30 November 2015 / Accepted: 8 December 2015 / Published: 12 December 2015
Cited by 6 | PDF Full-text (2315 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
The synthesis and reactivity of tetrazol-5-yl-phosphorus ylides towards N-halosuccinimide/TMSN3 reagent systems was explored, opening the way to new haloazidoalkenes bearing a tetrazol-5-yl substituent. These compounds were obtained as single isomers, except in one case. X-ray crystal structures were determined for three
[...] Read more.
The synthesis and reactivity of tetrazol-5-yl-phosphorus ylides towards N-halosuccinimide/TMSN3 reagent systems was explored, opening the way to new haloazidoalkenes bearing a tetrazol-5-yl substituent. These compounds were obtained as single isomers, except in one case. X-ray crystal structures were determined for three derivatives, establishing that the non-classical Wittig reaction leads to the selective synthesis of haloazidoalkenes with (Z)-configuration. The thermolysis of the haloazidoalkenes afforded new 2-halo-2-(tetrazol-5-yl)-2H-azirines in high yields. Thus, the reported synthetic methodologies gave access to important building blocks in organic synthesis, vinyl tetrazoles and 2-halo-2-(tetrazol-5-yl)-2H-azirine derivatives. Full article
(This article belongs to the Special Issue Organic Azides)
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Open AccessCommunication Synthesis, Characterization and Reactions of (Azidoethynyl)trimethylsilane
Molecules 2015, 20(12), 21328-21335; doi:10.3390/molecules201219770
Received: 9 November 2015 / Revised: 20 November 2015 / Accepted: 23 November 2015 / Published: 1 December 2015
Cited by 3 | PDF Full-text (1240 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Synthesis of azido(trimethylsilyl)acetylene (6) was performed by treating the iodonium salt 5 with highly soluble hexadecyltributylphosphonium azide (QN3) at −40 °C. Although this product is very unstable, it can nevertheless be trapped by the click reaction with cyclooctyne to
[...] Read more.
Synthesis of azido(trimethylsilyl)acetylene (6) was performed by treating the iodonium salt 5 with highly soluble hexadecyltributylphosphonium azide (QN3) at −40 °C. Although this product is very unstable, it can nevertheless be trapped by the click reaction with cyclooctyne to give the corresponding 1,2,3-triazole, and also directly characterized by 1H- and 13C-NMR data as well as IR-spectra, which were measured in solution at low temperature and in the gas phase. The thermal or photochemical decay of azide 6 leads to cyano(trimethylsilyl)carbene. This is demonstrated not only by quantum chemical calculations, but also by the trapping reactions with the help of isobutene. Full article
(This article belongs to the Special Issue Organic Azides)
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Open AccessArticle Towards the Synthesis of Graphene Azide from Graphene Oxide
Molecules 2015, 20(12), 21050-21057; doi:10.3390/molecules201219747
Received: 30 October 2015 / Revised: 17 November 2015 / Accepted: 18 November 2015 / Published: 26 November 2015
Cited by 3 | PDF Full-text (2039 KB) | HTML Full-text | XML Full-text
Abstract
In the last decades, organic azides haven proven to be very useful precursors in organic chemistry, for example in 1,3-dipolar cycloaddition reactions (click-chemistry). Likewise, azides can be introduced into graphene oxide with an almost intact carbon framework, namely oxo-functionalized graphene (oxo-G1),
[...] Read more.
In the last decades, organic azides haven proven to be very useful precursors in organic chemistry, for example in 1,3-dipolar cycloaddition reactions (click-chemistry). Likewise, azides can be introduced into graphene oxide with an almost intact carbon framework, namely oxo-functionalized graphene (oxo-G1), which is a highly oxidized graphene derivative and a powerful precursor for graphene that is suitable for electronic devices. The synthesis of a graphene derivative with exclusively azide groups (graphene azide) is however still a challenge. In comparison also hydrogenated graphene, called graphene or halogenated graphene remain challenging to synthesize. A route to graphene azide would be the desoxygenation of azide functionalized oxo-G1. Here we show how treatment of azide functionalized oxo-G1 with HCl enlarges the π-system and removes strongly adsorbed water and some oxo-functional groups. This development reflects one step towards graphene azide. Full article
(This article belongs to the Special Issue Organic Azides)

Review

Jump to: Research

Open AccessReview Azidation in the Difunctionalization of Olefins
Molecules 2016, 21(3), 352; doi:10.3390/molecules21030352
Received: 13 November 2015 / Revised: 12 February 2016 / Accepted: 9 March 2016 / Published: 16 March 2016
Cited by 18 | PDF Full-text (7253 KB) | HTML Full-text | XML Full-text
Abstract
Organic azides are key motifs in compounds of relevance to chemical biology, medicinal chemistry and materials science. In addition, they also serve as useful building blocks due to their remarkable reactivity. Therefore, the development of efficient protocols to synthesize these compounds is of
[...] Read more.
Organic azides are key motifs in compounds of relevance to chemical biology, medicinal chemistry and materials science. In addition, they also serve as useful building blocks due to their remarkable reactivity. Therefore, the development of efficient protocols to synthesize these compounds is of great significance. This paper reviews the major applications and development of azidation in difunctionalization of olefins using azide reagents. Full article
(This article belongs to the Special Issue Organic Azides)
Open AccessReview Synthesis and Chemistry of Organic Geminal Di- and Triazides
Molecules 2015, 20(11), 20042-20062; doi:10.3390/molecules201119675
Received: 5 October 2015 / Revised: 23 October 2015 / Accepted: 29 October 2015 / Published: 6 November 2015
Cited by 12 | PDF Full-text (4134 KB) | HTML Full-text | XML Full-text
Abstract
This review recapitulates all available literature dealing with the synthesis and reactivity of geminal organic di- and triazides. These compound classes are, to a large extent, unexplored despite their promising chemical properties and their simple preparation. In addition, the chemistry of carbonyl diazide
[...] Read more.
This review recapitulates all available literature dealing with the synthesis and reactivity of geminal organic di- and triazides. These compound classes are, to a large extent, unexplored despite their promising chemical properties and their simple preparation. In addition, the chemistry of carbonyl diazide (2) and tetraazidomethane (105) is described in separate sections. Full article
(This article belongs to the Special Issue Organic Azides)
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Open AccessReview Six-Membered Aromatic Polyazides: Synthesis and Application
Molecules 2015, 20(10), 19142-19171; doi:10.3390/molecules201019142
Received: 11 September 2015 / Revised: 30 September 2015 / Accepted: 13 October 2015 / Published: 21 October 2015
Cited by 9 | PDF Full-text (860 KB) | HTML Full-text | XML Full-text
Abstract
Aromatic polyazides are widely used as starting materials in organic synthesis and photochemical studies, as well as photoresists in microelectronics and as cross-linking agents in polymer chemistry. Some aromatic polyazides possess high antitumor activity, while many others are of considerable interest as high-energy
[...] Read more.
Aromatic polyazides are widely used as starting materials in organic synthesis and photochemical studies, as well as photoresists in microelectronics and as cross-linking agents in polymer chemistry. Some aromatic polyazides possess high antitumor activity, while many others are of considerable interest as high-energy materials and precursors of high-spin nitrenes and C3N4 carbon nitride nanomaterials. The use of aromatic polyazides in click-reactions may be a new promising direction in the design of various supramolecular systems possessing interesting chemical, physical and biological properties. This review is devoted to the synthesis, properties and applications of six-membered aromatic compounds containing three and more azido groups in the ring. Full article
(This article belongs to the Special Issue Organic Azides)
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