Reactions of 2-Unsubstituted 1H-Imidazole 3-Oxides with 2,2-Bis(trifluoromethyl)ethene-1,1-dicarbonitrile: A Stepwise 1,3-Dipolar Cycloaddition

Mlostoń, Grzegorz; Jasiński, Marcin; Linden, Anthony; Heimgartner, Heinz

doi:10.1002/hlca.200690129

Cited by 36 publications

(21 citation statements)

References 33 publications

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“…For example, a series of protein kinase inhibitors [4] was synthesized by the so-called ''sulfur transfer reaction'' [5], whereas direct palladium-catalyzed arylation protocol opened up direct access to potent Tie2 tyrosine kinase inhibitor [6]. Special attention was paid to the synthesis of imidazole N-oxides with new substitution patterns, particularly the analogs lacking a substituent at carbon C(2) atom, and their transformations into more complex derivatives [5,[7][8][9]. A large number of key 2-unsubstituted N-oxides exhibit limited stability either under high temperature, UV irradiation or in the presence of acylating agents, and can undergo isomerization to the corresponding imidazol-2-ones.…”

Section: Introductionmentioning

confidence: 99%

Temperature-dependent polymorphism of N-(4-fluorophenyl)-1,5-dimethyl-1H-imidazole-4-carboxamide 3-oxide: experimental and theoretical studies on intermolecular interactions in the crystal state

et al. 2014

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X-ray analysis of N-(4-fluorophenyl)-1,5-dimethyl-1H-imidazole-4-carboxamide 3-oxide reveals the temperature-dependent polymorphism associated with the crystallographic symmetry conversion. The observed crystal structure transformation corresponds to a symmetry reduction from I4 1 /a (I) to P4 3 (II) space groups. The phase transition mainly concerns the subtle but clearly noticeable reorganization of molecules in the crystal space, with the structure of individual molecules left almost unchanged. The Hirshfeld surface analysis shows that various intermolecular contacts play an important role in the crystal packing, revealing graphically the differences in spatial arrangements of the molecules in both polymorphs. The N-oxide oxygen atom acts as a formally negatively charged hydrogen bonding acceptor in intramolecular hydrogen bond of N-H…O -type. The combined crystallographic and theoretical DFT methods demonstrate that the observed intramolecular N-oxide N-H…O hydrogen bond should be classified as a very strong charge-assisted and closed-shell non-covalent interaction.

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Section: Introductionmentioning

confidence: 99%

Temperature-dependent polymorphism of N-(4-fluorophenyl)-1,5-dimethyl-1H-imidazole-4-carboxamide 3-oxide: experimental and theoretical studies on intermolecular interactions in the crystal state

et al. 2014

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“…Freshly prepared Raney-Ni has been shown to be an excellent deoxygenating agent for 1H-imidazole 3-oxides [12] [13]. Treatment of the (R)-and (S)-enantiomer of 7a and 7b with this reagent in MeOH at room temperature led to the corresponding 1H-imidazoles 10 within 30 min (TLC) in almost quantitative yield (Scheme 4).…”

Section: Methodsmentioning

confidence: 97%

“…Recently, some new methods for the synthesis of differently substituted imidazoles were described [6 -8]. Furthermore, in a series of papers, 2-unsubstituted imidazole 3-oxides were shown to be useful starting materials for the preparation of imidazole derivatives such as imidazole-2-thiones [9], imidazol-2-ones [10], 2-cyanoimidazoles [10], 2-(perfluoroethyl)imidazoles [11], 2-(dicyanomethylidene)imidazoles [12], as well as the parent imidazoles [12] [13].…”

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confidence: 99%

Synthesis of Optically Active 1‐(1‐Phenylethyl)‐1H‐imidazoles Derived from 1‐Phenylethylamine

Mlostoń

Mucha

Urbaniak

et al. 2008

Helvetica Chimica Acta

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The three-component reaction of (R)-or (S)-1-phenylethylamine (6), formaldehyde, and an a-(hydroxyimino) ketone 5, i.e., 3-(hydroxyimino)butan-2-one (5a) or 2-(hydroxyimino)-1,2-diphenylethanone (5b), yields the corresponding enantiomerically pure 1-(1-phenylethyl)-1H-imidazole 3-oxide 7 in high yield (Schemes 2 and 3). The reactions are carried out either in MeOH or in AcOH. Smooth transformations of the N-oxides into optically active 1-(1-phenylethyl)-1H-imidazoles 10 and 2,3-dihydro-1-(1-phenylethyl)-1H-imidazole-2-thiones 11 are achieved by treatment of 7 with Raney-Ni and 2,2,4,4-tetramethyl-3-thioxocyclobutanone (12), respectively (Scheme 4).

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“…Complexes of imidazoles [10] and imidazole derived carbenes [11] with diverse metal cations have also been studied extensively. In a series of recent papers, the synthesis of 2-unsubstituted imidazole N-oxides was reported [12][13][14][15].…”

Section: Introduction -mentioning

confidence: 99%

“…The formation of these products occurred via a regioselective [2+3]-cycloaddition to give 4 and subsequent fragmentation to produce 3 (Scheme 1). The reaction was proposed to proceed stepwise via a zwitterionic intermediate 5, which, in the presence of H 2 O, underwent the conversion to imidazol-2-ones [15].…”

Section: Introduction -mentioning

confidence: 99%

Synthesis of New Bis‐imidazole Derivatives

Jasiński

Mlostoń

Mucha

et al. 2007

Helvetica Chimica Acta

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The reaction of aldimines with alpha-(hydroxyimino) ketones of type 10 (1,2-diketone monooximes) was used to prepare 2-unsubstituted imidazole 3-oxides 11 bearing an alkanol chain at N(1) (Scheme 2, Table 1). These products were transformed into the corresponding 2H-imidazol-2-ones 13 and 2H-imidazole-2-thiones 14 by treatment with Ac2O and 2,2,4,4-tetramethylcyclobutane-1,3-dithione, respectively (Scheme 3). The three-component reaction of 10, formaldehyde, and an alkane-1,omega-diamine 15 gave the bis[1H-imidazole 3-oxides] 16 (Scheme 4, Table 2). With Ac2O, 2,2,4,4-tetramethylcyclobutane-1,3-dithione or Raney-Ni, the latter reacted to give the corresponding bis The reaction of aldimines with α-(hydroxyimino)ketones of type 10 (1,2-diketone monooximes) was used to prepare 2-unsubstituted imidazole 3-oxides 11 bearing a functionalized alkyl residue at N(1). These products were transformed into the corresponding imidazole-2-ones 13 and imidazole-2-thiones 14 by treatment with Ac 2 O and 2,2,4,4-tetramethylcyclobutane-1,3-dithione, respectively. The three-component reaction of 10, formaldehyde, and an alkane-1,ω-diamine 15 gave the bis-(imidazole 3-oxides) 16. With Ac 2 O, 2,2,4,4-tetramethylcyclobutane-1,3-dithione or Raney-Ni, the latter reacted to give the corresponding bis-(imidazol-2(3H)-ones) 19, bis-(imidazol-2(3H)-thiones) 20, and bis-imidazoles 22, respectively. The structures of 11a and 16bwere established by X-ray crystallography.

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Reactions of 2-Unsubstituted 1H-Imidazole 3-Oxides with 2,2-Bis(trifluoromethyl)ethene-1,1-dicarbonitrile: A Stepwise 1,3-Dipolar Cycloaddition

Cited by 36 publications

References 33 publications

Temperature-dependent polymorphism of N-(4-fluorophenyl)-1,5-dimethyl-1H-imidazole-4-carboxamide 3-oxide: experimental and theoretical studies on intermolecular interactions in the crystal state

Temperature-dependent polymorphism of N-(4-fluorophenyl)-1,5-dimethyl-1H-imidazole-4-carboxamide 3-oxide: experimental and theoretical studies on intermolecular interactions in the crystal state

Synthesis of Optically Active 1‐(1‐Phenylethyl)‐1H‐imidazoles Derived from 1‐Phenylethylamine

Synthesis of New Bis‐imidazole Derivatives

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