A reaction for the synthesis of benzimidazoles and 1H-imidazo[4,5-b]pyridines via a novel rearrangement of quinoxalinones and their aza-analogues when exposed to 1,2-arylenediamines

Мамедов, В. А.; Zhukova, Nataliya; Beschastnova, T. N.; Gubaidullin, А. Т.; Баландина, А. А.; Latypov, Shamil K.

doi:10.1016/j.tet.2010.10.026

Cited by 37 publications

(18 citation statements)

References 41 publications

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“…Benzimidazoylquinoxaline synthesis through a novel rearrangement in the reactions of 3-alkanoylquinoxalin-2-ones with 1,2-phenylenediamine according to Refs. [14] and [15]. lowed us to work at temperature of 140 8C.…”

Section: Resultsmentioning

confidence: 99%

“…Furthermore, if o-phenylenediamine with substituents was used in the first stage of this synthetic route, only one regioisomer of the target product was obtained, unlike what occurred for the synthetic route starting from glycerol described above or the synthetic routes starting from 3-hydroxyimino-2-butanone [11] or alkanoylquinoxalin-2-ones (see Scheme 2 and 4). [14,15] Entries 1-6 reveal the influence on the selectivity to 3 of the substituent of the diamine used in the second stage, which was responsible for the substituent present in the quinoxaline ring of the benzimidazoylquinoxaline product. Entries 7-12 reveal the influence of the diamine substituent in the first stage, which was responsible for the substituent present in the benzimidazole group.…”

Section: Scope Of the Reactionmentioning

confidence: 99%

“…[13] A recent alternative synthetic route for the synthesis of heteroarylquinoxalines with higher yields (72-97 %) involves the reaction between 3-alkanoylquinoxalin-2-ones with 1,2-phenylenediamine derivatives through a novel rearrangement (Scheme 2). [14,15] However the main drawback of this reaction procedure is the difficult synthesis of the alkanoylquinoxalin-2-Process intensification by using well-defined solid catalysts able to perform one-pot multistep reactions is one of the open fronts in heterogeneous catalysis. This is even more relevant if new, more efficient synthesis routes are open.…”

Section: Introductionmentioning

confidence: 99%

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Gold Catalysis Opens Up a New Route for the Synthesis of Benzimidazoylquinoxaline Derivatives from Biomass‐Derived Products (Glycerol)

et al. 2013

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The reaction of unsubstitued camphanyl‐piperazine 4 with ZnCl2, phenylacetylene, and benzaldehyde in toluene gave the corresponding dipropargylamine (i.e., 15) with opposite configurations at the newly formed stereogenic centres, which, upon reaction with ZnI2 resulted in the formation of a racemic mixture of 1,3‐diphenyl allene in 45 % yield. N‐Methylcamphanyl‐piperazine regioisomer 5, prepared by selective N‐methylation of the NH moiety attached to the stereogenic centre with (S)‐configuration, upon reaction with ZnCl2, phenylacetylene, and benzaldehyde in toluene, gave the corresponding propargylamine in 90 % yield, with an (S)‐configuration at the newly formed stereogenic centre, and upon subsequent reaction with ZnI2, this intermediate gave (R)‐1,3‐diphenyl allene in 52 % yield and with 96 % ee. Reaction of N‐methylcamphanyl‐piperazine isomer 5 with several 1‐alkynes and aldehydes in the presence of ZnBr2 gave the corresponding (R)‐allenes in 40–75 % yield and 79–99 % ee. In contrast, regioisomeric N‐methylcamphanyl‐piperazine 6 reacted with ZnBr2 to give the corresponding (S)‐allenes in 38–71 % yield and with 79–99 % ee. The opposite chiral discriminating abilities of the two NH moieties in camphanyl‐piperazines was confirmed by single‐crystal X‐ray analysis of the propargylamines formed. The results are discussed considering mechanisms involving the in situ formation of alkynylzinc halides, followed by diastereoselective addition to chiral iminium ion derivatives to give the corresponding propargylamines, and subsequent conversion to chiral allenes by an intramolecular 1,5‐hydrogen shift.

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Section: Resultsmentioning

confidence: 99%

Section: Scope Of the Reactionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Gold Catalysis Opens Up a New Route for the Synthesis of Benzimidazoylquinoxaline Derivatives from Biomass‐Derived Products (Glycerol)

et al. 2013

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“…Recently we have synthesized a series of 2-(benzimidazol-2yl)-3-arylquinoxalines 8 (Fig. 2), where the benzimidazole moiety, being the HB donor owing to its NH group, also includes another nitrogen atom immediately adjacent to the C-C link to the HB acceptor, i.e., the 3-arylquinoxaline moiety.…”

Section: Introductionmentioning

confidence: 99%

Benzimidazolylquinoxalines: novel fluorophores with tuneable sensitivity to solvent effects

Burganov

Zhukova

Мамедов

et al. 2017

Phys. Chem. Chem. Phys.

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We report on the photophysical properties, conjugation, conformational behavior, intra- and intermolecular hydrogen bonds (HBs) of a series of novel fluorophores, consisting of 3-arylquinoxaline and benzimidazole moieties linked by a single CC bond. Computations employing density functional theory (DFT) reveal that conjugation between these moieties stabilizes syn-conformers with two HB centers located on the same side of the molecule. Anti-conformers form stronger intermolecular HBs with DMSO and DMF than syn-conformers, and this influences the energy gap between syn- and anti-forms, especially upon excitation of the molecules to the S state. Substituents introduced in various positions of the molecules modify their conformational behavior, and mutual disposition of excited singlet states relative to the ground states. Various substitution patterns produce very different effects on relative quantum yield of luminescence: from a moderate increase in polar DMSO and DMF relative to 1,2-dichloroethane solutions to complete quenching of emission which is observable in polar media. The observed behavior is understood with the aid of DFT and time-dependent DFT calculations. The tuneability of the spectroscopic range of the luminescence and especially of its sensitivity to environmental effects allows rational design of the novel fluorophores of this family for various applications.

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“…Also, the synthesis of benzimidazoles by cyclization of Passerini reaction products in the presence of trifluoroacetic anhydride is known . Recently, a new method for the synthesis of 2‐hetaryl benzimidazoles by acid‐catalyzed quinoxaline–benzimidazole rearrangement was proposed .…”

Section: Introductionmentioning

confidence: 99%

Unexpected Formation of 5‐Nitro‐1H‐benzimidazoles by Nucleophilic Recyclization of 1‐Methyl‐5‐nitropyridinium Salts

Сагитуллина

Garkushenko

Novikov

et al. 2014

Journal of Heterocyclic Chem

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The synthesis of substituted 5‐nitro‐2‐phenyl‐1H‐benzimidazoles has been described via domino anionic process rearrangement of 3‐benzoylamino‐1,2‐dimethyl‐5‐nitropyridinium salts in the presence of NaOH water–alcohol solution. Substituted N‐benzoyl‐o‐phenylenediamines was obtained via recyclization of 3‐benzoylamino‐1,2‐dimethyl‐5‐nitropyridinium salts in the presence of aqueous methylamine solution.

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A reaction for the synthesis of benzimidazoles and 1H-imidazo[4,5-b]pyridines via a novel rearrangement of quinoxalinones and their aza-analogues when exposed to 1,2-arylenediamines

Cited by 37 publications

References 41 publications

Gold Catalysis Opens Up a New Route for the Synthesis of Benzimidazoylquinoxaline Derivatives from Biomass‐Derived Products (Glycerol)

Gold Catalysis Opens Up a New Route for the Synthesis of Benzimidazoylquinoxaline Derivatives from Biomass‐Derived Products (Glycerol)

Benzimidazolylquinoxalines: novel fluorophores with tuneable sensitivity to solvent effects

Unexpected Formation of 5‐Nitro‐1H‐benzimidazoles by Nucleophilic Recyclization of 1‐Methyl‐5‐nitropyridinium Salts

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