Thermolysis of geminal diazides: a novel route to 1,3,4-oxadiazoles

Ogilvie, William W.; Rank, Werner

doi:10.1139/v87-025

Cited by 44 publications

(14 citation statements)

References 4 publications

(5 reference statements)

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“…According to the authors, either the nitrene route with acyl migration in the intermediate 269 or an attack of the electron-rich nitrogen N-1 of the azide group on the carbonyl carbon giving zwitterion 270 may be considered in the formation of azidoazomethine 271 (Scheme 61). 109 The first photolysis of a-azido ketones was reported in 1964 by Edwards and Purushothaman. 75 The product of the irradiation of 2-azidocyclohexanone in hexane was assigned as 2-iminocyclohexanone on the basis of its IR characteristics, the easy polymerization of the obtained compound prevented the detailed structure elucidation.…”

Section: Thermolysis and Photolysis Of A-azido Ketonesmentioning

confidence: 99%

Syntheses and transformations of α-azido ketones and related derivatives

2011

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Organic azides are known and utilized in the synthetic organic chemistry as amine precursors, potential sources of nitrenes, dipoles useful in 1,3-dipolar cycloadditions and starting materials of phosphoranes for a long time, and their literature has been overviewed by several authors. On the other hand, there are some special subclasses within the azides which possess peculiar and interesting properties differing from those of the majority and offering extra synthetic possibilities. In this critical review we wish to give an exhaustive overview on the synthesis and synthetic potential of α-azido ketones and related systems, an underestimated group of compounds. The enhanced acidity of the α-hydrogen offers various new synthetic applications including the creation of a new C-C bond, while the joint presence of the carbonyl and vinyl functions of α-azido-α,β-unsaturated ketones results in a special reactivity, too. Chemo- and stereoselectivity issues also represent important points which are discussed in detail. Finally, the usefulness of the titled derivatives in the synthesis of various heterocycles is reviewed (273 references).

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Section: Thermolysis and Photolysis Of A-azido Ketonesmentioning

confidence: 99%

Syntheses and transformations of α-azido ketones and related derivatives

2011

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“…In the context of our ongoing research efforts, which concern the synthesis and reactivity of geminal di‐ and triazides, we realized that, in addition to the photochemical behavior of geminal diazides, a surprisingly small number of studies on the thermal decomposition of geminal diazides were reported . As we revised several of the early works on the thermolysis of geminal diazides, the study by Ogilvie and Rank reported in 1987 became the focus of our attention: A high‐yielding conversion of 2,2‐diazido acyl acetates 1 into 1,3,4‐oxadiazole‐2‐carboxylates 2 was described through simple heating of diazido starting compounds in xylene (Figure ) . The method does not require additional reagents and thus differs significantly from the alternative and more wide‐spread approaches toward this heterocyclic core, most of which are based on the chemistry of highly toxic hydrazides (Figure ) .…”

Section: Introductionmentioning

confidence: 98%

Synthesis of the 1,3,4‐Oxadiazole Core through Thermolysis of Geminal Diazides

2016

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The thermolysis of geminal diazides derived from acylacetate compounds is an efficient tool for the rapid construction of the 1,3,4‐oxadiazole core. While a broad range of ethyl esters undergoes smooth transformation to the desired heterocycles that contain the ester moiety in moderate to high yields, the analogous tert‐butyl esters give rise to the oxadiazoles with acyl groups, presumably through a pathway of decarboxylation followed by a new acyl transfer.

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“…In 1987, Rank and co‐workers [ 43 ] reported the surprising formation of the 1,3,4‐oxadiazole core through diazide thermolysis. Although the reaction was only tested with two substrates, leading to 26a and 26b (Scheme 8A), we showed decades later that this reaction is of general appeal, allowing for the oxadiazole synthesis with a reasonably broad scope (Scheme 8B).…”

Section: Reactivities Of Geminal Diazidesmentioning

confidence: 99%

Reactivity of Organic Geminal Diazides at Tetrahedral Carbons

Çelik

Kirsch

2020

Eur J Org Chem

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Organic compounds with geminal diazide units at sp3‐hybridized carbon atoms are a widely neglected class of compounds, with regard to their synthesis and their reactivities. In the last decade, we and others started to uncover reactivity patterns with this compound class, leading to new possibilities of reaction design. This minireview covers recent developments in the field, including the generation of heterocycles through thermolysis, the reactions with nucleophilic amines, and the hydrogenation.

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Thermolysis of geminal diazides: a novel route to 1,3,4-oxadiazoles

Abstract: The geminal diazides ethyl α,α-diazidoacetoacetate and α,α-diazidobenzoylacetate were prepared from the corresponding dibromo precursors by nucleophilic azide displacement. Thermolysis of the diazido compounds led to the formation of 2,5-disubstituted 1,3,4-oxadiazoles in high yield.

Cited by 44 publications

References 4 publications

Syntheses and transformations of α-azido ketones and related derivatives

Syntheses and transformations of α-azido ketones and related derivatives

Synthesis of the 1,3,4‐Oxadiazole Core through Thermolysis of Geminal Diazides

Reactivity of Organic Geminal Diazides at Tetrahedral Carbons

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