A new feature in the chemistry of nitrobenzofuroxans: ambident reactivity in Diels–Alder condensations

Hallé, Jean-Claude; Pouet, Marie‐José; Terrier, François; Vichard, Dominique; Huguet, Boris; Riou, D.

doi:10.1039/a800343b

Cited by 37 publications

(14 citation statements)

References 19 publications

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“…[13][14][15] The reaction of DNBF with cyclopentadiene (Cp) initially affords a 1:1 mixture of the two stereoselective [2+4] and [4+2] adducts 2 and 3 in their racemic forms. Addition of a second equivalent of Cp appears to favor reaction at the remaining nitro-activated C4=C5 bond in 3 rather than 2, which leads to an essentially quantitative formation of the highly functionalized diadduct 5 in racemic form.…”

Section: Introductionmentioning

confidence: 99%

The Stepwise Diels–Alder Reaction of 4‐Nitrobenzodifuroxan with Danishefsky’s Diene

Стегленко

Kletsky

Kurbatov

et al. 2011

Chemistry A European J

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The Diels-Alder reaction of 4-nitrobenzodifuroxan (NBDF) with 1-methoxy-3-trimethylsilyloxy-1,3-butadiene has been investigated experimentally and theoretically. Treatment of NBDF with excess diene in chloroform at room temperature was found to afford a single product that contained a carbonyl functionality. Based on an X-ray structure and NMR spectroscopic data, the product appeared to be a result of the hydrolysis of the OSiMe(3) moiety of the thermodynamically more stable endo [2+4] cycloadduct, characterized by a cis arrangement of the MeO and NO(2) functionalities. In situ NMR investigations of the interaction were carried out at room temperature in CDCl(3) and at -40 °C in deuterated acetonitrile. Calculations at the B3LYP/6-31G* level in the gas phase and in acetonitrile were carried out under the assumption that the most stable cis conformation of the diene is also the most reactive in the interaction. The analysis revealed the NBDF/cis diene interaction involves the formation of a zwitterionic intermediate. Importantly, this intermediate is formed in two preferred conformations, which correspond to the endo and exo modes of approach of the reagents. Cyclization of these two identified conformations afforded the experimentally characterized endo and exo [2+4] cycloadducts. According to the calculations, the interconversion of the two conformers can either take place through a return to the pre-reaction complexes or it can occur by rotation through an intermediate conformation of lesser stability. In view of the stepwise character of the interaction, the possibility that the intermediate zwitterion is the result of the interaction between NBDF and the trans diene could not be excluded. Calculations carried out with the most stable and more populated s-trans conformer confirmed this idea and supported the role of the zwitterion in the overall interaction.

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Section: Introductionmentioning

confidence: 99%

The Stepwise Diels–Alder Reaction of 4‐Nitrobenzodifuroxan with Danishefsky’s Diene

Стегленко

Kletsky

Kurbatov

et al. 2011

Chemistry A European J

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“…Additionally, there are a number of publications that deal with the incorporation of the heterocyclic rings into furazan and furoxan to construct complex molecules. These experimental [5,6] and theoretical [7][8][9] investigations show that furoxan has several important characteristics: high density, high positive heat of formation (HOF), and good oxygen balance. These characteristics make it an effective structural unit for designing new high energy density materials (HEDMs).…”

Section: Introductionmentioning

confidence: 98%

“…Many experimental and computational studies were centered on benzofuroxans [10][11][12], poly-furoxans on a chain or a circle [13][14][15][16][17][18][19][20], and macrocycles [6,[21][22][23][24][25], but single furoxan systems have been studied less extensively [4,[26][27][28][29][30]. Khmelnitskii and coworkers [30] reported the synthesis of 3,4-dinitrofuroxan (DNFX), a highly oxidized and fully nitrated heterocycle.…”

Section: Introductionmentioning

confidence: 99%

Theoretical studies of furoxan-based energetic nitrogen-rich compounds

et al. 2010

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Density functional theory calculations were performed to study the effects of different substituents and nitrogen-containing heterocyclic rings on the heats of formation (HOFs), energetic properties, and thermal stability for a series of furoxan derivatives. The isodesmic reaction method was employed to calculate the HOFs of the derivatives using total energies obtained from electronic structure calculations. The detonation velocities and pressures were evaluated by using the semiempirical KamletJacobs equations, based on the theoretical densities and HOFs. The bond dissociation energies and bond orders for the weakest bonds were analyzed to investigate the thermal stability of the furoxan derivatives. These results provide basic information for the molecular design of novel high energy density materials.

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“…Crucial evidence for this relationship has been the discovery that the nitro-activated double bonds of this ring behave similarly to nitroalkene fragments in a variety of Diels-Alder processes, acting as dienophiles or heterodienes depending upon the reaction partner and the experimental conditions at hand. [10][11][12][13][14][15][16] A first illustrative sequence refers to the reaction of ANBF with cyclohexadiene. Reflecting the potential 1-oxide/3-oxide interconversion of benzofuroxans through the intermediacy of an o-dinitroso intermediate, 15 diadducts 5 resulting from normal electron-demand Diels-Alder (NEDDA) processes involving the N=O double bonds of such intermediates as the dienophile contributors have also been isolated.…”

Section: Introductionmentioning

confidence: 99%

“…On the other hand, the preferred formation of the unsymmetrical IEDDA-NEDDA adduct 12 implies a greater dienophilic reactivity of the remaining nitroolefinic moiety in the IEDDA adduct 11 than in the NEDDA adduct 10. [10][11][12][13][14][15][16] 3.2 Elucidation of the reaction of DNBF with 2,3-dimethylbutadiene.…”

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confidence: 99%

NMR Spectroscopy: A Useful Tool in the Determination of the Electrophilic Character of Benzofuroxans - Case Examples of the Reactions of Nitrobenzofuroxans with Dienes and Nucleophiles

Sebban¹,

Sepulcri²,

Jovene³

et al. 2012

Magnetic Resonance Spectroscopy

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A new feature in the chemistry of nitrobenzofuroxans: ambident reactivity in Diels–Alder condensations

Cited by 37 publications

References 19 publications

The Stepwise Diels–Alder Reaction of 4‐Nitrobenzodifuroxan with Danishefsky’s Diene

The Stepwise Diels–Alder Reaction of 4‐Nitrobenzodifuroxan with Danishefsky’s Diene

Theoretical studies of furoxan-based energetic nitrogen-rich compounds

NMR Spectroscopy: A Useful Tool in the Determination of the Electrophilic Character of Benzofuroxans - Case Examples of the Reactions of Nitrobenzofuroxans with Dienes and Nucleophiles

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