The Chemistry of Unusually Functionalized Azides

Abstract

This short review describes the synthesis and reactions of organic azides bearing an adjacent additional functional group, such as azidoacetylenes, α-azido alcohols, geminal azidohalo compounds, formyl azide, 1,1-diazidoethenes, and azidocyclopentadienes. Some of these compounds were extensively investigated in previous quantum chemical studies, but experimental access was missing until quite recently; other such azides were simply overlooked for a long time. The title compounds are able to undergo a variety of intramolecular and intermolecular subsequent reactions, which can find application in synthetic chemistry. 1 Introduction 2 Ethynyl Azides 3 Geminal Azidohalo Compounds and α-Azido Alcohols 3.1 Azidohalomethanes 3.2 Discovery and Synthesis of α-Azido Alcohols 3.3 Reactions of α-Azido Alcohols 4 Formyl Azide 5 1,1-Diazidoethenes 6 Azidocyclopentadienes 7 Conclusion and Outlook

Synthesis and Characterization of Cyanobutadiene Isomers—Molecules of Astrochemical Significance

“…(Z)-1-Cyano-1,3-butadiene (Z-1). A selective route to produce (Z)-1-cyano-1,3-butadiene (Z-1) has been reported, 57 although details of the experimental procedure and spectroscopic properties are not readily available. Multiple studies describe the separation, isolation, and physical properties of Z-1.…”

“…56 (g) Banert. 57 The Journal of Organic Chemistry system (H 2 O/MeOH) in Scheme 1a was used in an attempt to optimize the solubility of the ionic and the organic reactants (sodium cyanide and 4-chloro-1,2-butadiene (7), respectively), but the formation of methanol adducts is clearly problematic. We changed the reaction solvent to acetonitrile, which seemed to be a more appropriate solvent for an S N 2 reaction.…”

Allylic azides: synthesis, reactivity, and the Winstein rearrangement

“…The rearrangement of propargyl azides was originally reported by Banert and has since been termed the Banert cascade (Scheme 45a). 4,161,[233][234][235][236][237][238] Much like the Winstein rearrangement, the Banert cascade starts with a [3,3]-sigmatropic rearrangement. This is followed by a 6-π electrocyclization and a nucleophilic trap to generate NH-1,2,3-triazoles.…”

“…In particular, the Huisgen cycloaddition, Staudinger reaction, Schmidt reaction, and Curtius rearrangement have been used extensively in organic synthesis. [1][2][3][4][5][6][7][8][9][10] Additionally, azides have classically been used as protected primary amine equivalents. The utility of organic azides has been further extended because of the bioorthogonality exhibited in several classic reactions with azides.…”

“…12 Because organic azides are useful synthetic intermediates, the general reactivity of organic azides has been reviewed several times. [1][2][3][4][5][6][7][8][9][10] The enormous breadth of azide reactivity can be divided into subclasses based on functionality adjacent to the azide. When additional functionality is proximal, the reactivity of an azide can change significantly.…”