Aziridines versus Vinyl Carbamates from the Direct Amination of Electron-Withdrawing Group-Substituted Trifluoromethyl Enoates

Fioravanti, Stefania; Colantoni, Daniele; Pellacani, Lucio; Tardella, Paolo A.

doi:10.1021/jo050044w

Cited by 36 publications

(20 citation statements)

References 30 publications

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“…Under homogeneous conditions [DABCO (1,4-diazabicyclo[2.2.2]octane)/CH 2 Cl 2 ] trifluoromethyl carbamates are obtained, while under heterogeneous conditions (NaH/THF) the only product is the aziridine (Scheme 62). This last compound might be formed through the expected aza-MIRC reaction, while a vinyl nitrene insertion reaction (favored by the homogeneous conditions) might be responsible for the N-protected enaminones [103].…”

Section: The Role Of Trifluoromethyl Groupmentioning

confidence: 99%

“…tert-Butyl nosyloxycarbamate [91,92,94,95,99,100,103,116,117] is the best reagent for the synthesis of short 2-cyano and 2-amido aziridinyl peptides (Scheme 70), interesting potential protease inhibitors, starting from a library of 2-L--amino acyl (E)-acrylonitriles [118], compounds structurally similar to tyrphostins.…”

Section: Other Nosyloxycarbamatesmentioning

confidence: 99%

“…Similarly, trifluoromethyl substituted imidazolinones (Scheme 74) have been obtained starting from trifluoromethyl -dicarbonyl compounds [100]. Benzyl [89,93,94,99,101,102,117] and 9-methylfluorenyl [86,94,103,117] nosyloxycarbamates were considered sometimes by us to introduce a nitrogen function carrying an easily removable group. Instead allyl aryloxycarbamates have been reported rarely [115,122].…”

Section: Other Nosyloxycarbamatesmentioning

confidence: 99%

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Ethyl Nosyloxycarbamate: A Chameleonic Aminating Agent

Pellacani¹,

Fioravanti²,

Tardella

2011

COC

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The purpose of this review is to illustrate the use of ethyl nosyloxycarbamate (NsONHCO(2)Et). This is a versatile aminating agent known for over 47 years and used to generate, in the presence of organic or inorganic bases under homogeneous conditions, a carbonyl nitrene, a reactive intermediate able to form new C-N or X-N bonds by electrophilic amination reaction of a remarkable variety of nucleophilic substrates. Interest in this reagent has been renewed most recently, during the past dozen years. Operating still in alkaline medium, but under generally heterogeneous conditions, has made possible new synthetic applications for the conjugate base of the same nosyloxycarbamate. These, developed mainly by our research group, allow to carry out direct syntheses of various nitrogenated compounds under mild conditions. The applications span from simple molecules to highly functionalized compounds and many new exciting regio- and stereoselective routes can be envisioned. In particular, it was possible to obtain aziridines containing a cornucopia of assorted functions and therefore able to provide access to more complex molecules under simple operational conditions by using an aminating agent cheap and easy to obtain

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Section: The Role Of Trifluoromethyl Groupmentioning

confidence: 99%

Section: Other Nosyloxycarbamatesmentioning

confidence: 99%

Section: Other Nosyloxycarbamatesmentioning

confidence: 99%

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Ethyl Nosyloxycarbamate: A Chameleonic Aminating Agent

Pellacani¹,

Fioravanti²,

Tardella

2011

COC

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“…For example, the N-methylation of indoles, the condensations of unsaturated aldehydes or ketones and the simple additions of alkyne [27,28,[42][43][44][45][46][47][48][49] To sum up, DABCO, as a small organic molecular catalyst has an important place in organic synthesis. Compared with the traditional transition-metal catalysts, DABCO is a widely used reagent which is stable, contamination-free, convenient and cheap.…”

Section: Application Of Dabco In Other Organic Synthesis Reactionsmentioning

confidence: 99%

Organic reactions catalyzed by 1, 4-diazabicyclo [2.2.2] octane (DABCO)

Yang

Tian

2008

Front. Chem. China

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The organic reactions catalyzed by 1, 4-diazabicyclo [2.2.2] octane (DABCO) are reviewed. Most of the reactions start conveniently from available substrate and proceed under mild conditions. The reactions are environmentally friendly and the catalyst can be recycled in some cases. The perspectives on DABCO-catalyzed reactions are pointed out. Keywords 1, 4-diazabicyclo [2.2.2] octane (DABCO), organic synthesis, catalysis 1,4-Diazabicyclo [2.2.2] octane (DABCO, Scheme 1), a cage-like compound, is a small diazabicyclic molecule, which has weak alkalescence, medium-hindrance and widely used in organic synthesis reactions. On the one hand, it can serve as a weak base and ligand, for example, reactions of the Nmethylation of indoles and Pd(OAc) 2 /DABCO-catalyzed Stille cross-coupling reaction, etc. On the other hand, it is also a very widely used catalyst in organic synthesis reactions, for example, the Baylis-Hillman reaction, synthesis of three-membered carbocyclic compounds and heterocyclic reactions containing oxygen, nitrogen. According to the types of products, this paper introduces the application of DABCO in organic synthesis in the recent years.

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“…A consequence of this would be the decomposition of o-NsN=IPh to o-NsNH 2 and PhI with the in situ formed sulfonamide subsequently initiating a iminoiodanemediated Michael-initiated ring closure (MIRC) reaction and product formation. [83][84][85][86][87][88] To verify this hypothesis as well as gain a better understanding of how the present aziridination process might proceed, we next conducted a series of control reactions with 3a (Scheme 2). In an initial control reaction, subjecting 3a to 20 mol% of DBU and 1.1 equiv of o-NsN=IPh in acetonitrile at room temperature for 18 h was found to afford 2b in 20% yield (Scheme 2a).…”

mentioning

confidence: 99%

Brønsted Base-Mediated Aziridination of 2-Alkyl-Substituted-1,3-Dicarbonyl Compounds and 2-Acyl-Substituted-1,4-Dicarbonyl Compounds by Iminoiodanes

et al. 2017

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The synthesis of α,α-diacylaziridines and α,α,β-triacylaziridines from reaction of 2-alkyl-substituted-1,3-dicarbonyl compounds and 2-acyl-substituted-1,4-dicarbonyl compounds with arylsulfonyliminoiodinanes (ArSO2N=IPh) under Brønsted base-mediated atmospheric conditions is described. The reaction mechanism is thought to involve the formal oxidation of the substrate followed by aziridination of the ensuing α,β-unsaturated intermediate by the hypervalent iodine(iii) reagent.

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Aziridines versus Vinyl Carbamates from the Direct Amination of Electron-Withdrawing Group-Substituted Trifluoromethyl Enoates

Cited by 36 publications

References 30 publications

Ethyl Nosyloxycarbamate: A Chameleonic Aminating Agent

Ethyl Nosyloxycarbamate: A Chameleonic Aminating Agent

Organic reactions catalyzed by 1, 4-diazabicyclo [2.2.2] octane (DABCO)

Brønsted Base-Mediated Aziridination of 2-Alkyl-Substituted-1,3-Dicarbonyl Compounds and 2-Acyl-Substituted-1,4-Dicarbonyl Compounds by Iminoiodanes

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