Synthesis of substituted furan-3-carboxylates from alkyl 3-bromo-3-nitroacrylates

Carbonyl-containing furan-3-carboxylates were obtained by the refluxing of alkyl 3-bromo-3-nitroacrylates and acyclic CH-acids, namely, pentane-2,4-dione and alkyl 3-oxo-butanoates in methanol in the presence of equimolar amounts of potassium acetate. The products can be prepared by the similar processing of 2-nitro-2,3-dihydrofuran-3-carboxy-lates being the intermediates in the total transformation.     

Reactions of methyl 3-hydroxythiophene-2-carboxylate. Part 4. Synthesis of methyl 5-azolyl-3-hydroxythiophene-2-carboxylates

The indirect introduction of an azolyl group in position 5 of compound 1 by an easy two-step procedure taking place at room temperature is described. A similar procedure yields the 4-chloro derivatives of these 5-azolyl compounds. The same method is applied for the introduction of a 5-azido group and from the 5-azido compounds, 5-v-triazolyl derivatives are obtained by a known method.     

Synthesis of substituted 3-nitroso-2,4-pyridinediols for use as analytical reagents

The 5-bromo, 5-iodo, and 5-nitro derivatives of 6-methyl-3-nitroso-2,4-pyridinediol were synthesized and shown to produce colored complexes with a number of Group VIII metal ions. Also synthesized were the 1-pentyl and 1-octyl esters of 4,6-dihydroxy-5-nitrosopyridine-3-carboxylic acid. These compounds showed potential as solvent extraction reagents for certain Group VIII metals.     

微波辐射下以1,3-二溴-5,5-二甲基乙内酰脲为溴代试剂合成3-溴黄酮

报道了在微波辐射下以1,3-二溴-5,5-二甲基乙内酰脲(DBDMH)为溴化试剂合成3-溴黄酮的新方法,系统考察了反应温度、时间及反应物配比对反应收率的影响.     

Synthesis of cucurbitine derivatives: facile straightforward approach to methyl 3-amino-4-aryl-1-methylpyrrolydine-3-carboxylates

A general three- or four-step synthesis of cis- and trans-substituted cucurbitine (3-aminopyrrolidine-3-carboxylic acid) derivatives from methyl 2-nitroacetate is reported. The first step utilizes a Knoevenagel condensation with five different aromatic imines or their corresponding aldehydes to form (Z/E)-mixtures of α-nitro acrylates. The second step gives rise to the pyrrolidine-core structures of the title compounds by a 1,3-dipolar cycloaddition reaction using an azomethine ylide. The last step consists of reduction of the nitro group to yield both diastereoisomers of the corresponding 4-aryl cucurbitine methyl esters.     

Synthesis of 4-aminomethyl-tetrahydrofuran-2-carboxylates with 2,4-cis and 2,4-trans relationships

Templated tetrahydrofuran-based γ-azido esters were prepared with the C-2 and C-4 functionalities in cis and trans relative configurations. This was achieved by ring contraction of the suitably protected 2-O-triflates of pentono-1,5-lactones (d-ribose and l-arabinose) with subsequent introduction of the azide via the 4-O-triflate. Access to a corresponding β-azido ester was achieved in good yield. Little elimination product was observed by introduction of the azide via the 3-O-triflate. These azido esters are scaffolds, which may be predisposed to adopt secondary structural motifs, for example, for use as peptidomimetics; they may also be utilised for the preparation of stereodiverse compound libraries.     

Synthesis of Alkyl 4-(1-Alkyl-2-aryl-2-oxoethyl)-5,5-dimethyl-2-oxotetrahydrofuran-3-carboxylates

Zinc enolates derived from 1-aryl-2-bromoalkanones react with alkyl 5,5-dimethyl-2-oxo-2,5-dihydrofuran-3-carboxylates to give alkyl 4-(1-alkyl-2-aryl-2-oxoethyl)-5,5-dimethyl-2-oxotetrahydrofuran-3-carboxylates. Reactions of the latter with amines, such as p-toluidine, cyclohexylamine, and piperidine, lead to the corresponding carboxamides.     

Synthesis of N3-substituted methyl exo-3,4-diazatricyclo[5.2.1.02,6]dec-4-ene-5-carboxylates

Reactions of methyl exo-3,4-diazatricyclo[5.2.1.0^2.6]dec-4-ene-5-carboxylate with methyl diazoacetate, methyl iodide, ethylene oxide, acetic acid, nitrosonium cation, and sulfur led to the formation of a series of N³-substituted exo-3,4-diazatricyclo[5.2.1.0^2,6]dec-4-enes.     

Three-component synthesis of methyl 6-alkyl-3-cyano-2-halopyridine-4-carboxylates

A procedure has been developed for the synthesis of methyl 6-alkyl-3-cyano-2-halopyridine-4-carboxylate by three-component reaction of 4-oxoalkane-1,1,2,2-tetracarbonitriles with hydrogen halides in methanol.     

Synthesis of 6-hetaryl-5,5-dialkyl-3,3-dimethyl-tetrahydropyran-2,4-diones by Reformatsky Reaction

Zinc enolates derived from ethyl 4-bromo-2,2,4-trimethyl-3-oxopentanoate and 4-bromo-4- ethyl-2,2-dimethyl-3-oxohexanoate react with 2-furan-, 2-thiophene-, 1-(3-nitrophenyl)-2-pyrrole-, 1-acyl-3-indole-, and 2-pyridinecarbaldehydes to give the corresponding 6-hetaryl-5,5-dialkyl-3,3-dimethyltetrahydropyran-2,4-diones.Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 10, 2004, pp. 1549–1551.Original Russian Text Copyright © 2004 by Shchepin, Korzun, Sazhneva.     

Thermal isomerization of 5-methoxy-3-arylisoxazoles to methyl 3-aryl-2H-azirine-2-carboxylates

The thermal isomerization of 5-methoxy-3-arylisoxazoles to methyl 3-aryl-2H-azirine-2-carboxylates was subjected to a kinetic study. A correlation between the isomerization rate constants and the ⁺ constants of the substituents in the aromatic ring is observed. The enthalpies of formation of a number of isoxazoles and 2H-azirines were calculated. The effect of the nature of the substituents on the mutual isomerization of isoxazoles and azirines is discussed. The results make it possible to refute the approved and previously proposed diradical mechanism for the isomeric transformations and are in agreement with a nitrene mechanism for the formation of azirines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1053–1056, August, 1978.     

Synthesis of benzyl and tert-butyl 3-(2-methoxycarbonylethyl)-4-methylpyrrole-2-carboxylates from methyl 4-oxobutanoate

Condensation of methyl 4-oxobutanoate with nitroethane in the presence of 4-dimethylaminopyridine, followed by treatment with acetic anhydride, afforded a nitroacetoxyester 10b . Subsequent reaction with isocyanoacetate esters and DBU in refluxing tetrahydrofuran gave the synthetically valuable pyrroles 1a and 1b.     

Synthesis of substituted pyrrolo[2,3-D]pyrimidine-2,4-diones

A facile route for the synthesis of substituted pyrrolo[2,3-d]pyrimidine-2,4-diones from substituted 2-amino-3-cyano-4-methylpyrroles is reported.     

Synthesis of 2-aryl-3-hydroxymethyl-5,5-difluoropiperidines

A strategy toward the synthesis of functionalized 5,5-difluoropiperidines, a class of compounds with potential as building block in medicinal chemistry, was developed. In a three-step procedure 2,2-difluoroglutaric anhydride was synthesized starting from ethyl bromodifluoroacetate. This key intermediate reacts fluently with various imines to yield 5,5-difluoropiperidinone carboxylic acids. Subsequent esterification of the obtained carboxylic acids enabled the isolation of trans-substituted 5,5-difluoro-2-arylpiperidinone-3-carboxylates as the major isomers. Reduction of the difluorinated piperidinonecarboxylates using borane gave rise to new trans-2-aryl-1-benzyl-5,5-difluoro-3-hydroxymethylpiperidines in excellent yields.