Facile synthesis of 3-trimethylsilylindazoles by [3+2]cycloaddition reaction of lithium trimethylsilyldiazomethane with benzynes

[3+2]Cycloaddition reaction of lithium trimethylsilyldiazomethane with benzynes, generated from halobenzenes, gave the corresponding 3-trimethylsilylindazoles in good to moderate yields.     

Direct synthesis of N-arylamides via the coupling of aryl diazonium tetrafluoroborates and nitriles under transition-metal-free conditions

The direct synthesis of N-arylamides via the coupling of aryl diazonium tetrafluoroborates and nitriles under transition-metal-free conditions has been developed. The reported protocol is practical and represents an efficient method to produce functionalized amides in moderate to good yields.     

Transition-metal-free,atom-economical cascade synthesis of novel 2-sulfonated-benzo[f][1,7]naphthyridines and their cytotoxic activities

An efficient, transition-metal-free cascade synthetic method has been developed for new 2-aryl/heteroaryl sulfonated benzo[f][1,7]naphthyridines. It is tert-butyl hydroperoxide (TBHP) mediated highly regioselective sulfonylation?cyclization?aromatization process between N-(3-aryl/heteroarylprop-2-yn-1-yl)quinolin-3-amines and aryl/heteroaryl sulfonylhydrazides. This synthetic protocol offers one-step strategy for CS and CC bond formations with a broad range of functional group tolerance. It is a simple, mild, and atom-economical route for the synthesis of various valuable functionalized 1, 2-aryl/heteroaryl sulfonated benzo[f][1,7]naphthyridines in moderate yields. Since the core motif of 2-sulfonated benzo[f][1,7]naphthyridines are biologically and pharmaceutically important (TLR activity 7, 8 modulators). Additionally, the synthesized derivatives were evaluated for their in vitro cytotoxic activities against six human cancer cell lines including lung (NCIH23), colon (HCT15), gastric (NUCG-3), renal (ACHN), prostate (PC-3), and breast (MDA-MB-231) cell lines. These compounds displayed significant cytotoxic activities against all tested human cancer cell lines.     

Transition-metal-free synthesis of primary to tertiary carboxamides: A quick access to prodrug-pyrazinecarboxamide

One-pot expedient and direct carbamoylation of heterocyclics is described. The transformation is realized via direct dehydrogenative aminocarbonylation of heterocyclic compounds under transition-metal-free conditions. This method is regioselective and the protocol is proved to be scalable on a gram scale. Further, the therapeutically useful antitubercular agent pyrazinecarboxamide is successfully synthesized by employing this protocol.     

Interaction of secondary amines with aromatic aldehydes-efficient method for synthesis of the functionalized heterocyclic amines

A method is proposed for the benzylation of secondary heterocyclic amines with functionalized derivatives of benzaldehyde in the presence of formic acid under conditions close to amination according to the Leuckart-Wallach reaction. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1820–1823, December, 2007.     

Transition-metal-free phenylselenylation of arenes with triflic anhydride activated methyl phenyl selenoxide

Phenylselenylation of arenes were achieved in a one-pot procedure by treating arene substrates with triflic anhydride activated methyl phenyl selenoxide, and then demethylation with diisopropylamine. This reaction provide a convenient method to prepare diarylselenide products under transition-metal-free conditions.

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CuCl-catalyzed aerobic oxidative reaction of primary aromatic amines

The oxidations of primary aromatic amines were investigated. Cuprous chloride-air system can catalyze the oxidation of primary aromatic amines to azo derivatives, anils, and/or quinone anils. The experimental procedure is simple and the products could be easily isolated in high yields.     

Preparation of amphiphilic sucrose carbamates by reaction with alkyl isocyanates in water-alcohol mixtures

The reactivity of sucrose with isocyanates in aqueous media has been studied. Mixtures of water and alcohols allow good conversion of the isocyanates to sucrose carbamates. The influence of the reaction parameters on the selectivity (degree of substitution and regioselectivity) was investigated in the case of long chain isocyanates, which have potential surfactant properties.     

An efficient carbapenem synthesis via an intramolecular Wittig reaction of new trialkoxyphosphorane-thiolesters

New trialkoxyphosphorane-thiolesters 10, obtained by reaction of oxalimides 9 with trialkyl phosphite, were efficiently cyclized by an intramolecular Wittig reaction to give carbapenems 11.     

One-step,stereoselective synthesis of octahydrochromanes via the Prins reaction and their cannabinoid activities

Novel, functionalized octahydrochromane derivatives were synthesized in a single step via the Prins reaction. Enantiomerically pure (+)-isopulegol was reacted with benzaldehyde to stereoselectively yield the corresponding octahydro-2H-chromen-4-ol derivative containing five stereocenters. A total of 10 compounds were synthesized by altering the enantiomer of isopulegol and the substituted benzaldehyde, and the resulting enantiopure octahydrochromanes were screened in vitro against the cannabinoid receptor isoforms CB1 and CB2. Compounds containing an olefin at the C4 position [(+)-3c, (?)-3c, (?)-7c, (?)-9c and (?)-11c] of the octahydrochromane scaffold were found to exhibit reasonable displacement of [³H] CP55,940 from the CB receptors, whereas the corresponding hydroxy analogs [(+)-3a, (+)-3b, (?)-3a, (?)-3b and (+)-5a] had very little or no effect.     

The reaction of pentachloropyridine with aromatic amines

The reaction of pentachloropyridine with aromatic amines in dimethylformamide in the presence of sodium carbonate leads to 4-arylaminotetrachloropyridines. The product of the reaction of pentachloropyridine with aniline in pyridine is 4-amino-2,3,5,6-tetrachloropyridine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 7, pp. 963–965, July, 1970.     

Direct arylation of tertiary amines via aryne intermediates using diaryliodonium salts

With a strategy by using diaryliodonium salts as the precursors of benzynes, direct N-arylation of tertiary amines with diaryliodonium salts was reported. Thus, the desired aromatic tertiary amines with a wide range of substituents were synthesized in moderate to excellent yields of 55–91%.     

Spectrophotometric determination of aromatic amines by reaction with p-benzoquinone

A comprehensive study is made of the application of the p-benzoquinone spectrophotometric technique to the aromatic amines. The technique involves a reaction with excess p-benzoquinone; the colored products display maximum absorption at 490–510 nm (varying according to the type of the amine used) and E_{1 cm}^1% in the range of 90–380. On the basis of an IR investigation, ethyl alcohol has been selected as a suitable solvent medium for aromatic amine determination. Electron-donating groups react faster and give more intense color than do electron-withdrawing groups. Results with an average recovery of 95% and mean standard deviation of 3.4% are obtained with seven aromatic amines.     

Transition-metal-free sp3 C–H activation of 2-methylquinoline with terminal alkynes for synthesis of 3-(quinolin-2-yl)isoxazoles

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On the reaction of 2-chloroethylisothiocyanate with aromatic amines

The reaction of aromatic amines with 2-chloroethylisothiocyanate 2 to give 2-arylaminothiazolines 1 was investigated. The course of this reaction was found to depend on the electronic nature of the amine and the reaction conditions. With arylamines that are relatively electron-rich, good yields of the thiazolines 1 were obtained. With electron-poor amines, adducts 4 , in which two equivalents of 2 reacted with the amine, accompanied 1. The relative amounts of 2:1 adducts increased as the arylamine became progressively more electron deficient. With 3,4-dichloroaniline, the yields of the 2:1 adducts were promoted by the presence of triethylamine.     

One-pot synthesis of substituted indolo[1,2-a]quinolines under transition-metal-free conditions

A simple and efficient one-pot synthesis of substituted indolo[1,2-a]quinolines under transition-metal-free conditions has been developed. When 2-fluorobenzaldehyde was treated with substituted 2-methylindoles in the presence of Cs₂CO₃, the desired products were typically obtained in good to excellent yields. This reaction sequence involves a nucleophilic aromatic substitution and a Knoevenagel condensation reaction. Our mechanistic investigation revealed that both reactions could proceed as an intermolecular reaction in the first step.     

Synthesis of enantiomerically-enriched N-aryl amino-amides via a Jocic-type reaction

Enantiomerically-enriched secondary trichloromethyl-alcohols react with aryl amines to give enantiomerically-enriched α-N-arylamino-acid derivatives. The intermediate acid chlorides can react in situ with aryl or, regioselectively, with alkyl amines to give aryl or alkyl α-N-arylamino amides.     

Efficient and economic halogenation of aryl amines via arenediazonium tosylate salts

Arenediazonium tosylate salts have been successfully employed as a new and efficient reagent in halogenation reactions. A novel and economic protocol has been developed for the bromination and chlorination of various anilines using arenediazonium tosylate salts. A wide variety of reaction conditions were studied in acetonitrile at either room temperature or 60 °C in the presence or absence of catalyst with good to excellent yields. A surprising result showed the formation of acetanilides as a major product of aniline and methyl-substituted aniline halogenations in high yields.     

Catalyst-free alkanoylation of aromatic rings via arylstannanes. Scope and limitations

The reaction of alkanoyl chlorides with arylstannanes in 1,2-dichlorobenzene (180 °C) is a simple and direct route for the catalyst-free and regioselective synthesis of tertiary alkyl aryl ketones in good to excellent isolated yields (55-77%). Nevertheless, under similar conditions, reactions carried out with alkanoyl chlorides bearing α-hydrogens render only the product of protodestannylation.