M. A. Yurovskaya

Cycloaddition to buckminsterfullerene C60: advancements and future prospects

Investigations on mono-[2+1]-, -[2+2]-, -[2+3]-, -[2+4]-, and polycycloaddition to [60]fullerene are reviewed. The main reagents used in cycloaddition and the reaction mechanisms are surveyed. The possible applications of cycloadducts are considered. The review covers the investigations of the last five years as well as the most important earlier studies.

Synthesis of N-substituted indole-3-carboxylic acid derivatives via Cu(I)-catalyzed intramolecular amination of aryl bromides.

A variety of N-alkylated and N-arylated derivatives of methyl 1 H-indole-3-carboxylate were synthesized efficiently via Ullmann-type intramolecular arylamination, using the CuI-K 3PO 4-DMF system. This catalytic amination procedure can be performed with good to high yields under mild conditions under an air atmosphere.

Chemistry of indoles

It is shown on the basis of data from the UV and IR spectra that keto acids of the indole series exist in the open acid form. The anomalies in the spectral behavior in alkaline media are determined by the formation of an anion involving the indole hydrogen atom.

Cycloaddition reaction of 1-(4-nitrophenyl)-3-phenylnitrile ylide to buckminsterfullerene[60]

Abstract Cycloaddition of 1-(4-nitrophenyl)-3-phenylnitrile ylide generated in situ from N-benzyl-4-nitrobenzimidoyl chloride to C 60 yields to 1,2-[3,4-dihydro-2-phenyl-5-(4-nitrophenyl)-2 H - pyrrolo]-[60]fullerene and diastereomeric mixture of two 5,6-open isomers. Moreover, double carbon-nitrogen bond of 5,6-open of adduct is located in α position to unsubstituted phenyl ring.

One-pot synthesis of substituted indoles via titanium(IV) alkoxide mediated imine formation – copper-catalyzed N-arylation

Readily accessible o-bromobenzylketones and primary alkyl amines and anilines were used for the construction of substituted indoles in good to excellent yields. The sequence involves a titanium-mediated reaction of ketones with amines to afford imines and subsequent intramolecular cyclization into indoles employing copper catalysis. The two-step protocol allows for the preparation of indoles bearing both N-alkyl and N-aryl groups as well as N-unsubstituted indoles without isolation of the intermediates and is tolerant of a wide range of functionality.

Regioselective synthesis and crystal structure of C70(CF3)10[C(CO2Et)2]

The Bingel reaction of poly(trifluoromethyl)fullerene p7mp-C70(CF3)10 with diethyl malonate and CBr4 in the presence of bases yields the C70(CF3)10[C(CO2Et)2] cycloadduct as a major product, along with two C70(CF3)10[CH(CO2Et)] isomers. An XRD study of the main compound demonstrates that a [2 + 1] cycloaddition occurs at the unoccupied pole of the p7mp-C70(CF3)10 molecule. The observed regiochemical selectivity of the [2 + 1] cycloaddition is shown to be favored from both energetic and orbital reactivity viewpoints.

New strategies for the synthesis of N-alkylated indoles (Review)

New data, mostly published in the last five years, on methods for the synthesis of N-alkylated indoles both as a result of direct introduction of the alkyl substituent at the nitrogen atom and by construction of the indole heterocyclic system are reviewed. Only examples of indole derivatives containing branched, sterically hindered, and chiral alkyl substituents at the nitrogen atom are discussed.

Stereoselective reduction of endocyclic carbon–nitrogen double bond: application to the synthesis of biomolecules

Abstract Recent advances in the stereoselective synthesis of nitrogen containing heterocyclic compounds using the reduction of endocyclic double carbon–nitrogen bond are surveyed.

Heterocyclic derivatives of fullerene C60. 1: Synthesis of new fulleropyrazolines by the 1,3-dipolar cycloaddition of nitrile imines

New stable [6,6]-closed cycloadducts, fulleropyrazolines containing aryl, hetaryl, trifluoromethyl, and other substituents in the five-membered ring, have been obtained by the 1,3-dipolar cycloaddition of nitrile imines to C60. Two methods of generating nitrile imines in situ have been used, the dehydrohalogenation of the corresponding hydrazonoyl halides by the action of triethylamine and the thermal decomposition of 2,5-diaryltetrazoles.

Indoles from 3-nitropyridinium salts: A new route to chiral indoles and indolines

Abstract (S)-1-(1-Methylbenzyl)-2,4,6-trimethylindole was prepared by interaction of (S)-isopropyliden(1-methylbenzyl)amine with 1,2,4,6-tetramethyl-3-nitropyridinium iodide. The indoles thus prepared undergo diastereoselective hydride reduction and debenzylation to afford chiral (S)-2,4,6-trimethylindoline with high yield and optical purity up to 76%.