基于碳-氢键转化的吲哚硫醚类化合物合成研究进展

吲哚硫醚类化合物是吲哚衍生物中常见和重要的化合物,合成这类化合物的常用方法是通过吲哚3-位碳-氢键的直接官能团化。在过去的十来年时间,这类合成方法的相关研究发展迅猛,大量新型高效的催化和合成策略被报道,使得人们在合成吲哚硫醚类化合物方面具有的越来越多的选择。本文主要综述近几年通过碳-氢键转化合成吲哚-3-硫醚类化合物的合成研究进展。     

吲哚咔唑类化合物生物合成途径研究进展

以雷别卡霉素和星形孢菌素为主要对象,陈述其合成过程中的基因、酶和中间产物。吲哚咔唑类化合物的生物合成主要分为吲哚环的形成、糖基的形成以及两者的连接。起始物色氨酸经过色氨酸修饰、双吲哚吡咯的形成和氧化环的闭合形成吲哚环,通过糖基转移酶将吲哚咔唑核心和糖基连接合成目标化合物。     

吲哚类抗肿瘤药物的研究进展

吲哚类化合物足较重要的一类杂环衍生物生物碱,多数具有显著生理活性:近年来人们合成了大量的新型吲哚类化合物,并对其作用机制进行了研究,本文综述了吲哚-3-甲醇类、5-甲氧基吲哚类、吲哚-3-甲醛类、氮取代的吲哚类等四种吲哚类抗肿瘤药物的研究进展,并分析了当前抗肿瘤药物所存在的问题及发展前景.     

吲哚环化合物的经典合成方法及研究进展

吲哚类化合物是一种重要的化工原料,在医药、化工、农业、染料等很多领域有着非常重要的用途。本文综述了吲哚环类化合物的经典合成方法及近年来的合成上的研究进展。     

醋酸钯催化直接芳基化合成2-芳基吲哚类化合物

为探究操作简便、绿色经济、底物适用性强的合成2-苯基吲哚类化合物的新方法,对反应溶剂、催化剂种类及用量、氧化剂种类和反应温度等反应条件进行筛选,选取最佳反应条件对取代吲哚及取代苯硼酸进行底物适用性实验,并进行结构表征。实验得到以物质的量分数为10%的Pd(OAc)₂为催化剂,物质的量分数为20%的Cu(OAc)₂为氧化剂,冰乙酸为溶剂,室温反应8 h为最佳反应条件,共合成了23个2-芳基吲哚类化合物,产率高达87%。本实验开发了一步合成2-芳基吲哚类化合物的方法,该方法对不同取代的吲哚和苯硼酸均具有较好的适用性,与已报道的方法相比,本方法具有底物适用性强、产率高、操作简便、经济环保等优点,为2-芳基吲哚类化合物的制备提供了更加高效的路径。     

由吲哚合成氧代吲哚啉类化合物的方法研究进展

氧代吲哚啉类化合物是一类重要的精细化工中间体,广泛存在于医药、农药、天然产物等的分子骨架结构中,开发其合成的新方法具有重要的价值。通过吲哚的氧化反应,合成氧代吲哚啉类化合物,是最直接、高效的合成方式。本文着重综述了近年来吲哚氧化合成氧代吲哚啉的方法。文章还结合目前此领域的前沿现状,分析了各种合成方法存在的不足和缺陷,并在课题组研究工作的基础上,提出了合成此类化合物研究前景和展望。     

3-吡咯氧化吲哚参与不对称构建手性季碳中心的研究进展

氮杂季碳手性中心结构存在于许多生物活性分子或药物分子中,C3位含有氮原子的3,3'-二-取代氧化吲哚结构更是许多具有生物活性的天然产物或药物分子的核心骨架,以3-吡咯氧化吲哚作为亲核试剂不对称合成结构多样的3,3'-二取代氧化吲哚类化合物是一种可行的构建含氮杂季碳手性中心化合物的方法.综述了3-吡咯氧化吲哚通过分子内反应和分子间反应两种形式参与构建3,3'-二取代氧化吲哚类化合物的研究进展,并对构建含氮杂季碳手性中心化合物进行了展望.     

3-吡咯氧化吲哚参与不对称构建手性季碳中心的研究进展

氮杂季碳手性中心结构存在于许多生物活性分子或药物分子中,C3位含有氮原子的3,3'-二-取代氧化吲哚结构更是许多具有生物活性的天然产物或药物分子的核心骨架,以3-吡咯氧化吲哚作为亲核试剂不对称合成结构多样的3,3'-二取代氧化吲哚类化合物是一种可行的构建含氮杂季碳手性中心化合物的方法.综述了3-吡咯氧化吲哚通过分子内反应和分子间反应两种形式参与构建3,3'-二取代氧化吲哚类化合物的研究进展,并对构建含氮杂季碳手性中心化合物进行了展望.     

吲哚类抗癌化合物的研究进展

吲哚类化合物因其广泛的生物活性在抗癌药物领域备受关注。将不同修饰基团引入吲哚结构中,能产生一系列具有抗癌活性的化合物,它在抗癌药物的开发中发挥越来越重要的作用。根据吲哚化合物的不同结构分类综述了其在抗癌领域的研究进展,并对研究趋势进行了展望。     

磷酸二苯酯催化的2-吲哚甲烷胺衍生物的合成

以磷酸二苯酯为催化剂,3-甲基吲哚类化合物与亚胺通过Friedel-Crafts加成反应一步合成了具有广泛药理活性的2-吲哚基甲烷胺类化合物,对反应条件进行优化.结果表明,当n(3-甲基吲哚类化合物):n(亚胺化合物):n(磷酸二苯酯)=1.0:2.0:0.1,其中,当以0.0025 mmol磷酸二苯酯为催化剂,1 mL无水二氯甲烷为溶剂,室温下反应30 min时,即可得到高收率2-吲哚基甲烷胺类衍生物(85％～90％).产物经1HNMR、13CNMR和HRMS进行了结构确定,并推测了反应机理.     

A new route to 4-, 5-, and 6-indolecarboxylic acids

There are many indole derivatives bearing carboxyl or methoxycarbonyl groups on the benzene ring and these often have patent physiological activities. Synthesis of these compounds usually starts from indoles having a halogen group at the desired position on an indole ring. We now report a facile synthesis of 4-, 5-, and 6-indolecarboxylic acids from 2-bromoaniline derivatives ( 1 ). The synthetic route is shown in Figure 1.     

7-取代吲哚类化合物合成及官能团化研究进展

7-取代吲哚化合物是合成药物及精细化学品的重要中间体.本文综述了近15年金属Pd催化的7-取代吲哚化合物的制备方法,将其分成直接合成法和吲哚7位官能团化法两类,对每一类的反应过程和机理进行了详细介绍和评述.     

Manganese Chloride as an Efficient Catalyst for Selective Transformations of Indoles in the Presence of a Keto Carbonyl Group

Catalysis by manganese chloride tetrahydrate was found to be effective for the selective transformation of indoles, with which the desired acid‐catalyzed reaction could be promoted and, at the same time, a side reaction that also needs assistance of acid, the electrophilic reaction of indole with the co‐existing keto carbonyl group, does not occur. Some acid‐catalyzed reactions, such as the ring‐opening reaction of 2‐alkoxy‐3,4‐dihydropyran with indole, and transesterification of β‐keto ester with an alcohol that contains a C‐3 unsubstituted indole fragment, could be performed smoothly by using manganese chloride as catalyst. A new multicomponent reaction of indole, 3,4‐dihydropyran and β‐keto ester was also developed with catalysis by manganese chloride.     

Copper‐Catalyzed Activation of Dioxygen: Oxidative Cyclization of 2‐Arylindoles

A series of unusual six‐ring‐fused heterocycles containing indole and quinoline skeletons was successfully synthesized by a copper‐catalyzed reaction from 2‐arylated indoles. Two new bonds were regioselectively formed from C H and C H coupling. ¹⁸O‐Labelled experiments revealed that the dioxygen is not only the oxidant but also the reactant.     

Novel Enantiocomplementary C2‐Symmetric Chiral Bis(imidazoline) Ligands: Highly Enantioselective Friedel–Crafts Alkylation of Indoles with Ethyl 3,3,3‐Trifluoropyruvate

Enantioselective Friedel–Crafts alkylations of a variety of indoles with ethyl 3,3,3‐trifluoropyruvate catalyzed by novel chiral m‐phenylenebis(imidazoline)‐copper(II) complexes or the bis(imidazoline)‐achiral acid combination afforded products with high enantioselectivity. Both enantiomers of indole derivatives can be prepared with high enantioselectivities by tuning the N‐substituents of the imidazoline.     

Sorption of Indoles by Montmorillonite

Infra-red spectra supported by chemical, differential thermal and X-ray analyses indicate that indole and methylated indoles are sorbed by variously substituted montmorillonites in seven different configurations. The type of configuration formed depends upon the indoles and the interlayer cations. It affects the layer separation and the thermal stability of the assemblages.     

过渡金属Pd在吲哚及其衍生物合成中的应用

吲哚及其衍生物是一类非常重要的杂环类精细化工中间体。由于Pd催化剂的突出的优越性能,如反应条件温和、活性高、选择性好,在合成吲哚及其衍生物时获得了广泛应用。综述了近几年来的应用发展情况。     

Asymmetric Friedel–Crafts Reaction of Indoles with Ethyl Trifluoropyruvate Using a Copper(I)‐Bisoxazolidine Catalyst

Bisoxazolidine 1 is an effective ligand in the copper(I)‐catalyzed Friedel–Crafts reaction of alkyl trifluoropyruvates and indoles. A range of ethyl 2‐(3′‐indolyl)‐3,3,3‐trifluoro‐2‐hydroxypropanoates was produced in up to 99% yield and 94% ee within 30 min to 4 h. The effect of temperature on conversion and enantioselectivity proved to be substrate specific and was optimized individually. Of particular interest is that this method tolerates the presence of substituents in various positions in the indole ring. Yields ranging from 90–97% and ee values between 90 and 94% were obtained at optimized temperatures with substrates carrying substituents in position 1 or 7.     

Extent of thermal decomposition of indole glucosinolates during the processing of canola seed

A series of samples representing various stages of canola seed processing were obtained from two commercial processing plants to assess the extent of thermal degradation of indole glucosinolates during the crushing process. The individual glucosinolate content of all samples was determined along with the content of indole glucosinolate thermal degradation products [indoleacetonitriles and thiocyanate ion (SCN)]. Only minor decomposition of indole glucosinolates was evident prior to the desolventization stage of seed processing. Major decomposition of indole glucosinolates occurred in the desolventization of seed processing with little or no effect during meal drying. Indoleacetonitriles (3-indoleacetonitrile and 4-hydroxy-3-indoleacetonitrile) and SCN together accounted for 45–60% of the degraded indoles in the samples studied.     

A New Indole Synthesis Promoted by Metal Triflates

A new synthesis of 4- and 7-carbon-substituted indoles is described. The overall sequence involves the addition of a nitrile oxide to 1 carboethoxy-2-(or 3-) allylpyrrole, hydrogenation of the intermediate isoxazoline to β-hydroxy ketone and cyclization of the ketol using magnesium or zinc triflate to the substituted indole. This new indole-forming strategy can also accommodate the introduction of oxygen functionality into the indole 6-position. Possible mechanistic aspects of the reaction are detailed.