Green Aspect for Multicomponent Synthesis of Spiro[4H-indeno[1,2-b]pyridine-4,3′-[3H]indoles]

An efficient, four-component reaction of isatin, 1,3-indanedione, ethyl acetoacetate, and ammonium acetate in ethanol/water (9:1) system furnished spiro[4H-indeno[1,2-b]pyridine-4,3′-[3H]indoles] at room temperature. Merits of the method are mild reaction conditions, simple workup procedure, and ambient temperature. The synthesized compounds exhibit excellent fluorescence properties.     

Design, synthesis and antiproliferative activities of novel 5H-pyridazino[4,5-b]indoles

A novel series of 5H-pyridazino[4,5-b]indoles were designed and synthesized in order to find novel potent anticancer compounds.The structures were confirmed by ~1H NMR and MS.Their antiproliferative activities against two cancer cell lines were tested by the MTT method in vitro.Three of compounds (1e,1g,and 1h) exhibited potent antiproliferative activities,especially compound 1h (with IC_(50) values of 5.2μmol/L and 1.9μmol/L against Bel-7402 and HT-1080,respectively).The preliminary structure-activity relationships of 5H-pyridazino[4,5-b]indole derivatives were discussed.     

Synthesis of 2,4-disubstituted pyrimido[4,5-b]-indoles,pyrano[4′,3′:4,5]pyrrolo[2,3-d]pyrimidines and some conversions of pyrimido[4,5-d]indoles

Methods have been developed for the production of 2,4-disubstituted 5,6,7,8-tetrahydro-9H-pyrimido[4,5-b]indoles and pyrano[43:4,5]pyrrolo[2,3-d]pyrimidines. Heterocyclization reactions were carried out on 4-hydrazinopyrimido[4,5-b]indoles.A. L. Mndzhoyan Institute of Fine Organic Chemistry, National Academy of Sciences of the Republic of Armenia, Erevan, 375014. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10. pp. 1413–1416, October, 1996. Original article submitted June 21, 1996.     

Sterically Controlled Regiospecific Cyclization of Aldose-5-ethyl-1,2,4-triazino[5,6-b]indol-3-ylhydrazones to Linearly Annelated 3-Polyhydroxyalkyl-10-ethyl-1,2,4-triazolo-[4′,3′:2,3]-1,2,4-triazino[5,6-b]indoles

Summary.  Condensation of aldoses with 5-ethyl-3-hydrazino-1,2,4-triazino[5,6-b ]indole gave the corresponding aldose-5-ethyl-1,2,4-triazino[5,6-b ]indol-3-ylhydrazones which were acetylated to their poly-O-acetyl derivatives. The latter underwent sterically controlled regiospecific oxidative cyclization with bromine in acetic acid and sodium acetate to sterically favourable linearly annelated 3-polyacetoxyalkyl-10-ethyl-1,2,4-triazole[4′,3′:2,3]-1,2,4-triazino[5,6-b ]indoles rather than to their sterically unfavourable angularly annelated regioisomers. The regiospecific outcome of this heterocyclization is discussed in terms of electronic as well as steric factors, and the assigned structures have been corroborated on the basis of chemical as well as spectroscopic evidence. De-O-acetylation of the acetoxyindoles with ammonium hydroxide in methanol gave the title compounds. Representative members of the prepared compounds were tested for antimicrobial activity. Received November 3, 1999. Accepted December 13, 1999     

Straightforward Bienaymé and copper catalyzed N-arylation sequence to access diverse 5H-pyrido[2′,1′:2,3]imidazo[4,5-b]indoles and analogues

A two-step sequence is reported giving access to diverse 5H-pyrido[2′,1′:2,3]imidazo[4,5-b]indoles and analogues via a Bienaymé multicomponent reaction followed by N-arylation. The desired polycylic scaffolds were obtained in high yield using copper iodide in association with TMEDA in aqueous or dioxane media.     

苯并咪唑并[2,1-b]噻唑衍生物的合成

以2-巯基咪唑类化合物为原料,室温下与含有端基炔的二芳基高碘盐反应,一步合成苯并咪唑并[2,1-b]噻唑衍生物,其结构经¹H NMR、¹³C NMR、 单晶X-衍射和HR-MS表征。在最佳反应条件［n(2-巯基苯并咪唑)/n(二芳基高碘盐)=1/1,二氯甲烷为溶剂,反应12 h］下,目标化合物的产率最高为84%。同时对该反应的机理进行了详细探讨,并采用MTT法研究了目标化合物对人肝癌细胞（HepG2）生长情况的影响。结果表明：当浓度为4 μg/mL时,化合物3b具有较强的抑制HepG2细胞增殖的活性,抑制率为52%。     

Catalytic asymmetric dipolar cycloadditions of indolyl delocalized metal-allyl species for the enantioselective synthesis of cyclopenta[b]indoles and pyrrolo[1,2-α]indoles

The development of novel synthons and efficient methods to synthesize chiral polycyclic indoles has been a hot topic in organic synthesis and medicinal chemistry owing to their broad applications in medicines,pesticides,and other functional molecules.Here,we disclosed novel indolyl substituted metal-allyl zwitterionic intermediates through the decarboxylation of conveniently available vinyl indoloxazolidones,which could be regarded as two types of dipolar species through the anionic delocalization.The palladium-π-allyl species tended to serve as an all-carbon 1,3-dipole in the asymmetric[3+2]cycloaddition with electrondeficient alkenes,which furnished polysubstituted cyclopenta[b]indoles with high regio-and stereoselectivities.Meanwhile,the iridium-π-allyl species was recognized as an aza-1,3-dipole in asymmetric[3+2]cycloaddition with in situ generated C1 ammonium enolates,affording pyrrolo[1,2-α]indoles with high diastereo-and enantioselectivities.In addition,the dipolar cycloadditions could be easily scaled-up and several synthetic transformations of the cycloadducts were demonstrated for the rapid synthesis of diverse chiral polycyclic indoles.     

Engaging thieno[2,3-b]indole-2,3-dione for the efficient synthesis of spiro[indoline-3,4′-thiopyrano[2,3-b]indole] by reaction with N-substituted isatilidenes

A simple and efficient method, proceeding through a new mechanistic pathway, for the synthesis of spiro[indoline-3,4-thiopyrano[2.3-b]indole derivatives have been developed by exploiting the reaction of thieno[2,3-b]indole-2,3-dione with N-substituted isatilidenes. The compounds synthesized have been screened for antibacterial activity. The generality of the reaction and mechanistic rationale are presented.     

Synthesis of Some New Thieno[2,3-b]pyridines,Pyrimidino[4′,5′:4,5]thieno[2,3-b]-pyridines,and 2,3-Dihydro-1,3,4-thiadiazoles

Thieno[2,3-b]pyridines were synthesized from 6-benzofuran-2-yl-4-phenyl-2-sulfanylpyridine-3-carbonitrile and each of chloro acetone, ethyl chloroacetate, ω -bromoacetophenone, and chloroacetonitrile. These compounds were conveniently converted into novel pyrido[4′,5′:4,5]thieno[3,2-d]pyrimidines. Also, 2,3-dihydro-1,3,4-thiadiazole was synthesized from hydrazonoyl halides and 2-benzofuran-2-yl-3-(phenylamino)-3-thioxopropanenitrile. The structures of the products have been elucidated by elemental analyses, spectral data studies, and alternative syntheses whenever possible. The newly synthesized compounds were tested towards microorganisms.     

A new phenanthro [2,3-b] furan from Pleione bulbocodioides

A novel phenanthro[2,3-b]furan 1,named(3-hydroxy-9-(4′-hydroxy-3′-methoxypheny1)-11-methoxy-5,6,9,10-tetrahydro- phenanthro[2,3-b]furan-10-yl)methyl acetate,and two known phenolic compounds were isolated from the tubers of Pleione bulbocodioides(Franch.)Rolfe.Their structures were elucidated by spectroscopic methods.     

新型[1,2,4]三唑[4,3-b]均四嗪类化合物的合成及其抗癌活性

以6-(3,5-二甲基吡唑-1-基)-3-肼基均四嗪和芳醛为原料,经Schiff碱缩合和环合反应合成了6个新型的6-芳基-3-(3,5-二甲基吡唑-1-基)[1,2,4]三唑[4,3-b]均四嗪类化合物(4a～4f),其结构经1HNMR,MS,IR和元素分析表征。以顺铂为对照,采用MTT法测试了体外4a～4f对人白血病细胞株,人肺癌,人乳腺癌和人子宫颈癌细胞株的抗癌活性。结果表明,4a～4f对四种癌细胞均具有较强的抑制活性。     

异色满并[4,3-b]喹啉衍生物的合成

早在1931年,Hetherington等从念珠状曲菌(Aspergillus Cand inin)和土曲菌(Asperillus tereus)等菌类中分离出带有异色满(Isochroman)环系结构的左旋抗菌素橘霉素(C itrinin),后来又相继发现诸多带有异色满环系的天然产物[1-3],新近在软木木质素中也发现了多种具有异色满结构的     

Synthesis of Benzo[4,5]furo[3,2-b]thieno[2,3-d]pyridines —Derivatives of a New Heterocyclic System

Russian Journal of Organic Chemistry - Methyl 2-(bromomethyl)thiophene-3-carboxylates reacted with substituted 2-hydroxybenzonitriles to give methyl...     

不对称合成Tetrahydropyrano[3,4-b]indoles:两价钯催化的氮钯化/1,4-加成串联反应

正Angew.Chem.Int.Ed.2017,56,14698~14701Tetrahydropyrano[3,4-b]indoles(THPIs)具有重要的生物和生理活性.这类化合物的合成方法较多,但基本都是从吲哚出发经几步完成,其中不对称合成的例子也较少,尤其是过渡金属催化的方法.中国科学院上海有机化学研究所金属有机化学国家重点实验室陆熙炎课题组多年来一直致力于两价钯催化的、无氧化还原过程的新反应的研究.     

Synthesis of Bisindolylindeno[1,2-b]quinoxaline and Bisindolylindeno[3,4-b]pyrazine with Poly(N,N′-dibromo-N-ethylnaphthyl-2,7-disulfonamide)

Poly(N,N′-dibromo-N-ethylnaphthyl-2,7-disulfonamide) (PBNS) as novel reagent was synthesized. Bisindolylindeno[1,2-b]quinoxaline and bisindolylindeno[3,4-b]pyrazine derivatives were synthesized in a simple and efficient method from the three-component condensation reaction of indole, indane-1,2,3-trione, and diamine aromatic compounds by PBNS under solvent-free conditions at 80 °C in good to excellent yields, short reaction times, and a simple procedure for new derivatives.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications^® for the following free supplemental resource(s): Full experimental and spectral details.]     

铜催化偶联反应高效合成苯并[4,5]咪唑并[1,2-b]吡唑衍生物

建立了一种快速、高效的CuI催化N-(2-溴芳基)-5-苯基-1H-吡唑-3-胺发生分子内C—N偶联反应合成苯并[4,5]咪唑并[1,2-b]吡唑衍生物的新方法.该方法以廉价的CuI/杂环烯酮缩胺为催化剂,在二甲基亚砜(DMSO)中反应只需10min,具有反应迅速、操作简便、合成效率高等优点.     

香豆素并[4,3-d]噻吩[3,2-b:5,4-b']双吡啶衍生物的合成

以4-氯甲基香豆素为基础物质,通过与3-氰基-2-吡啶硫酮的烷基化及Thorpe-Ziegler反应,得到4-(3-氨基噻吩并[2,3-b]吡啶-2-基)香豆素,接着在对甲苯磺酸作用下,通过Picter-Spengler反应与芳香醛进行缩合,以良好收率合成了一系列香豆素并[4,3-d]噻吩[3,2-b:5,4-b']双吡啶衍生物。该反应操作简单、条件温和、收率良好。产物结构经NMR,IR,MS及元素分析数据得以证实。     

Unexpected Recyclization of 1H-δ-Carbolines to Pyrrolo[1,2-a]indoles

When 1H-2-methyl-1-p-nitrophenyl-3-ethoxycarbonylpyrido[3,2-b]indole (1) is heated in alcoholic solutions of ammonia, we observe a previously unknown recyclization leading to formation of 2-alkoxycarbonyl-3-methyl-9-p-nitrophenylimino-9H-pyrrolo[1,2-a]indoles (3,6).     

Synthesis of Green Colored Photochromic 6′-Arylamino Spiro [2H]Naphth[1,2-b]oxazines

The published route to a series of 6′-arylamino substituted photochromic spirooxazines has been investigated with improvements made to perform the synthesis in satisfactory yield. The route has been exemplified with several novel derivatives prepared (including hydroxyl functionalised). Additionally, a one-pot procedure for the conversion of suitably functionalized 1,2-naphthoquinones into the photochromic compounds is reported.     

含有异噁唑的S-三唑[3,4-b]-1,3,4-噻二嗪、咪唑[2,1-b]-1,3,4-噻二唑和咪唑[2,1-b]-1,3,4-噁二唑衍生物的合成

异噁唑衍生物作为一类重要的生物活性物质,其合成一直受到人们的关注,其中德国HMR公司开发研制的新型抗内风湿性关节炎药来氟米特(Leftunomide)已于1998年在美国率先上市,该药还具有很好的免疫调节作用．7H-均三唑[3,4-b]-1,3,4-噻二嗪、咪唑并[2,1-b]噻唑和咪唑并[2,1-b]-1,3,4-噻二唑衍生物均表现出广谱的生物活性．