A Calorimetric Investigation To Safely Scale-Up a Curtius Rearrangement of Acryloyl Azide

Ende, David J. am; DeVries, Keith M.; Clifford, and Pamela J.; Brenek, Steven J.

doi:10.1021/op970115w

Cited by 53 publications

(39 citation statements)

References 6 publications

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“…18,19 The structures of the products were established using IR, 1 H-NMR, 13 C-NMR and high resolution mass spectroscopy. Pilot thermolysis of the carbonyl azides 1-3 and 5 (1 mmol) at 220 °C for 15 minutes in anhydrous hexadecane (1 dm -3 ) led to the corresponding isocyanates 1a-3a and 5a.…”

Section: Resultsmentioning

confidence: 99%

“…This technique is known to provide information which is valuable for the planning of thermochemical reactions that involve organic azides 12 or acryloyl azides. 13 This work was undertaken with a view to uncovering new evidence supporting the direct applicability of the CR to the synthesis of amines from carboxylic acids. Our long-standing interest in nitrogen pseudo-halogens such as azides and isocyanates arises from their utility in the synthesis of nitrogen-linked heteroaryls.…”

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confidence: 99%

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The conversion of furan-, thiophene- and selenophene-2-carbonyl azides into isocyanates: a DSC analysis

Salatelli¹,

Zanirato²

2002

Arkivoc

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Abstract:The Curtius Rearrangement (CR) of five heteroaroyl azides to the corresponding isocyanates was studied by Differential Scanning Calorimetry. The five compounds selected were the furan 1, the thiophene 2, 5-methylthiophene 3, 5-(trimethylsilyl)thiophene 4, and selenophene-2-carbonyl azide 5. For each compound, the heat of the transition from the heteroaroyl azide to the isocyanate was measured by DSC under a set of standard conditions both in the absence and presence of an inert medium.

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Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

The conversion of furan-, thiophene- and selenophene-2-carbonyl azides into isocyanates: a DSC analysis

Salatelli¹,

Zanirato²

2002

Arkivoc

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“…The Curtius rearrangement converts acyl azides into isocyanates [100,109]. This has been used in flow chemistry [110], for example, for the preparation of PARP-1 inhibitors [111].…”

Section: Organic Reactions Of Azidesmentioning

confidence: 99%

Hydrazoic Acid and Azides

Bräse

Mende

Jobelius³

et al. 2015

Ullmann's Encyclopedia of Industrial Chemistry

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“…Unfortunately, this rearrangement has the drawback that low molar mass acyl azides present an explosion hazard. 7 This safety issue has limited the industrial use of this transformation until recently, when Am Ende et al 8 reported a new experimental protocol, which enabled the use of this reaction under safer conditions even when conducted on a large scale. This and other protocols have revived interest in this rearrangement, particularly for industrial purposes.…”

Section: Introductionmentioning

confidence: 99%

Hyphenating the curtius rearrangement with Morita-Baylis-Hillman adducts: synthesis of biologically active acyloins and vicinal aminoalcohols

Amarante¹,

Cavallaro²,

Coelho³

2011

J. Braz. Chem. Soc.

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Um rearranjo de Curtius, utilizando adutos de Morita-Baylis-Hillman como substrato, foi realizado em uma sequência que permitiu a síntese de várias hidroxi-cetonas (aciloínas) com uma grande diversidade estrutural e com bons rendimentos globais. Por sua vez, essas aciloínas foram transformadas em 1,2-amino-alcoóis de configuração relativa anti, através de uma etapa de aminação redutiva altamente diastereosseletiva. A utilidade sintética dessas abordagens foi demonstrada através das sínteses totais da (±)-bupropiona, fármaco utilizado no tratamento na síndrome de abstinência de fumantes e da (±)-espisulosina, um potente agente anti-tumoral isolado inicialmente de uma fonte marinha.Using Morita-Baylis-Hillman adducts as substrates, the Curtius rearrangement was performed in a sequence that allowed the synthesis of several hydroxy-ketones (acyloins) with great structural diversity and in good overall yields. These acyloins in turn were easily transformed into 1,2-anti aminoalcohols through a highly diastereoselective reductive amination step. The synthetic utility of these approaches was exemplified by performing the syntheses of (±)-bupropion, a drug used to treat the abstinence syndrome of smoker and (±)-spisulosine, a potent anti-tumoral compound originally isolated from a marine source. Keywords:Curtius rearrangement, Morita-Baylis-Hillman, drugs, aminoalcohols, acyloins IntroductionThe formation of new C-N bonds by incorporation of a nitrogen atom into a molecule is a fundamental transformation in organic chemistry, since it allows accessing many valuable compounds. 1 Basically, this can be achieved by nucleophilic substitution reactions or by electrophilic amination reactions. 2 A C-N bond can also be built through rearrangement reactions. For instance, Lossen, 3 Beckman, 4 Schmidt 5 and Curtius 6 rearrangements are processes which allow the efficient formation of a new C-N bond from carbonyl containing derivative compounds.The Curtius rearrangement is a thermal decomposition of a carbonyl azide leading to an isocyanate. This stereospecific rearrangement provides carbamates or amines in good overall yields and selectivities. Unfortunately, this rearrangement has the drawback that low molar mass acyl azides present an explosion hazard. 7 This safety issue has limited the industrial use of this transformation until recently, when Am Ende et al. 8 reported a new experimental protocol, which enabled the use of this reaction under safer conditions even when conducted on a large scale. This and other protocols have revived interest in this rearrangement, particularly for industrial purposes. 9 Regarding the potential of this rearrangement, our group has recently reported the preparation of some carbamates from Morita-Baylis-Hillman (MBH) adducts. 10 Curtius rearrangement would be the best way to achieve our target, since the carboxyl group in this structure is needed to perform this rearrangement. Thus, when an acid derived from a MBH adduct was treated with sodium azide, heated at reflux and treated subsequently w...

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A Calorimetric Investigation To Safely Scale-Up a Curtius Rearrangement of Acryloyl Azide

Cited by 53 publications

References 6 publications

The conversion of furan-, thiophene- and selenophene-2-carbonyl azides into isocyanates: a DSC analysis

The conversion of furan-, thiophene- and selenophene-2-carbonyl azides into isocyanates: a DSC analysis

Hydrazoic Acid and Azides

Hyphenating the curtius rearrangement with Morita-Baylis-Hillman adducts: synthesis of biologically active acyloins and vicinal aminoalcohols

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