17β-雄甾醇-[3,2-b]-吲哚的合成

以表雄酮为原料,经羟基氧化、羰基保护、还原、Fischer吲哚环化等反应合成了17-β-醇-雄甾-[3,2-b]-吲哚(5),总收率43.2%,其结构经1H NMR,IR和MS确证。生物活性初步测试结果表明:与雄诺龙相比,5对淡色库蚊的杀虫活性显著提高,在浓度为400 mg·L-1时,杀虫率为41.5%。     

One-pot sequential multi-component reaction: Synthesis of 3-substituted indoles

Here, we have developed a 3-component one-pot sequential approach to 3-substituted indoles. The main advantages of this process are step economy, reduced waste, and operational simplicity. The method involves in situ generation of 3-indolylalcohols from the reaction of indoles and aldehydes in the presence of base. Further, nucleophilic substitution of 3-indolylalcohols with various nucleophiles affords 3-substituted indole derivatives. The reaction does not requires any hazardous and expensive metal catalyst. In addition, the reaction is carried out in (1:1) ethanol–water which is considered as environmentally benign solvent. On the other hand, nonsequential 3-component reaction results in the formation of unwanted bisindolylmethanes.     

2-Bromo-i-phenylethylidenemalononitrile in the synthesis of thieno[3,2-b]pyridines and thiazolo[4,5-b]pyridines

A novel regioselective synthesis of thieno[3, 2-blpyridines and thiazolo[4,5-blpyridines from 2-bromo-I-phenyl ethylidenemalononitrile is proposed. In the case of the thiazolo[4, 5-b]pyridines, the intermediate 5-(2, 2-dicyano-l-phenylvinyl)thiazoles were separated. Formation of the thiazolo(4,5-b]pyridines was confirmed by x-ray analysis.A. D. Zelinski Institute of Organic Synthesis, Russian Academy of Sciences, Moscow 117913. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 413–419, March, 1996. Original article submitted December 22, 1995.     

New method for the synthesis of substituted thieno[3,2-b]pyridines and 5H-pyrano[2,3-d]thieno[3,2-b]pyridines derived from them

A new highly selective method was developed for the synthesis of substituted thieno[3,2-b]-pyridines based on the domino reaction of monopotassium salt (rather than dipotassium one) of carbamoylcyanodithioacetic acid with ethyl 4-chloroacetoacetate. Substituted 5H-pyrano[2,3-d]-thieno[3,2-b]pyridines were synthesized based on these thieno[3,2-b]pyridines.     

Efficient synthesis of substituted thieno[3,2-e]indoles

Efficient cyclization reactions of 5-aminobenzothiophene derivatives with internal and terminal acetylenes, giving 7- and 8-substituted thieno[3,2-e]indoles, are described. The reaction of 4-iodo-5-(methylsulfonamido)benzothiophene with terminal alkynes gave 7-substituted thienoindoles using general Sonogashira reaction conditions. Reaction of 5-amino-4-iodobenzothiophene with internal acetylenes, using Larock's heterocyclization reaction conditions, gave 7,8-disubstituted thieno[3,2-e]indoles.     

Facile synthesis of 3-substituted thieno[3,2-b]furan derivatives

A facile synthesis of dimethyl 3-hydroxythieno[3,2-b]furan-2,5-dicarboxylate is reported from the available methyl thioglycolate and dimethyl acetylenedicarboxylate starting materials. This compound represents an efficient precursor for the synthesis of 3-substituted thieno[3,2-b]furan derivatives.     

Synthesis of 3-substituted cyclopenta[b]indoles

When reacting with I₂, 2-(cyclopent-2-enyl)anilines undergo cyclization into 3-iodo-1,2,3,3a,4,8b-hexahydrocyclopenta[b]indoles in high yields. The minor reaction products were 3,5- or 3,7-diiodoindolines. Ammonolysis of 3-iodo-5-methyl-1,2,3,3a,4,8b-hexahydro-cyclopenta[b]indole or itsN-chloroacetyl derivative results in 3-amino-5-methyl-1,2,3,3a,48b-hexahydro- and 5-methyl-1,3a,4,8b-tetrahydrocyclopenta[b]indoles. Published inIzvestiya Akademii Nauk. Seriya Khimischeskaya, No. 10, pp. 1789–1793, October, 2000.     

Convenient synthesis of melatonin analogues: 2- and 3-substituted -N-acetylindolylalkylamines

A new method for the synthesis of 2- and 3-substituted indolylalkylamides, derivatives of melatonin, from arylhydrazines and amidoketones by the Fischer reaction was elaborated. The amidoketones can be easily prepared from cyclic imines by reaction with acylpyridinium chloride. This method is a one-step synchronous creation of the selected alkylamide fragment and the indole core. Variation of the arylhydrazines create the desired substituents in the carbocycle of indolylalkylamides and suitable choice of amidoketone can direct the amidoalkyl chain to the 2- or 3-position of the indole.     

One-pot synthesis of 4,6-diaryl-3-cyanopyridine-2(1H)-thiones and their transformation to substituted thieno[2,3-b;4,5-b]dipyridines and pyrido[3",2":4,5]thieno[3,2-d]pyrimidines

4,6-Diaryl-3-cyanopyridine-2(1H)-thiones were synthesized in one step by the reaction of elemental sulfur, malononitrile, and 2-aryl-1-aroylethylenes in the presence of excess triethylamine. The products were used in one-pot syntheses of substituted thieno[2,3-b;4,5-b]dipyridines and pyrido[3",2":4,5]thieno[3,2-d]pyrimidines.     

General synthesis of dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT) derivatives

A new straightforward synthesis of dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT) derivatives from readily available 2-methoxynaphthalenes is described. Thus, newly developed derivatives of DNTT showed very high field effect mobility in the vapor-processed field-effect transistors up to 8 cm(2) V(-1) s(-1).     

New method of synthesis of δ-carbolines from 3-indolinone via pyrano[3,2-b]indoles

2-Arylidene-1-acetylindolin-3-ones were obtained from 1-acetylindolin-3-ones and p-substituted benzaldehydes or 4-pyridinecarboxaldehyde, by the action of malonodinitrile, andwere converted into 2-amino-4-aryl-5-acetyl-3-cyanopyrano[3,2-b]indoles. When heated with an aqueous-alcoholic solution of KOH, the latter compounds transform into 2-alkoxy-4-aryl-3-cyano--carbolines. The possible paths of formation of -carbolines and pyrano[3,2-b]indoles are discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 230–235, February, 1985.     

Expedient synthesis of indoles from N-Boc arylhydrazines

The readily available N-Boc arylhydrazines undergo efficient Fischer cyclizations to provide the indoles in good yields, when reacted with enolizable ketones.     

Convenient synthesis of substituted 3-aminothiophene-2-carbonitriles from α-acetylenic nitriles and their conversion to thieno[3,2-d]pyrimidines

Several novel 2,4,6-trisubstituted thieno[3,2-d]pyrimidines were synthesized from the hitherto unknown 3-amino-5-methyl-(or 5-phenyl)thiophene-2-carbonitriles 7 and 8 . o-Aminonitriles 7 and 8 were obtained in a single step by conjugate addition of mercaptoacetonitrile (generated in situ) to substituted acetylenic nitriles 4 and 5 and annelation of the intermediate vinylic thioethers.     

Synthesis of functional 2-substituted 4-phenyl-9H-pyrimido[4,5-b]indoles

A method was developed for the synthesis of 2-oxo-4-phenyl-2,3-dihydro-9H-pyrimido[4,5-b]indole as well as of 2-chloro- and 2-nitramino-4-phenylpyrimido[4,5-b]indoles. The replacement of the chlorine atom in 2-chloropyrimidoindole gave rise to a number of its functional derivatives (morpholino, azido, and cyano). The reaction of 2-chloro-substituted pyrimidoindole with hydrazine hydrate and catalytic hydrogenation of 2-nitraminopyrimidoindole were studied.     

One-pot diastereoselective synthesis of tetrahydroepimino-benzo[b]azocines through sequential [3+2]-cycloaddition and Staudinger-aza-Wittig reactions

The one-pot synthesis of tetrahydro-epiminobenzo[b]azocines through a sequential 1,3-dipolar cycloaddition and intramolecular Staudinger-aza-Wittig reaction sequence is reported. This methodology provides a new and efficient approach for medium-sized and bridged nitrogen heterocyclic molecules.     

Synthesis and properties of [1,4]diazepino[6,5-b]indoles

1-Aryl-2-oxo-1,2,3,6-tetrahydro[1,4]diazepino[6,5-b]indole N-oxides were synthesized based on 3-(N"-aryl-N"-chloroacetyl)amino-2-formylindoles. Deoxidation of 2-oxo-1-phenyl-1,2,3,6-tetrahydro[1,4]diazepino[6,5-b]indole N-oxide afforded 1,2,3,6-tetrahydro- and 1,2,3,4,5,6-hexahydro[1,4]diazepino[6,5-b]indole derivatives. A new approach to the synthesis of pyrido[3,2-b]indole and pyrimido[5,4-b]indole derivatives was developed.