过渡金属催化苯并咪唑衍生物的合成研究进展

苯并咪唑衍生物具有多种生物活性,在医药、农药等领域有着广泛的应用,该类化合物的合成也是当前的研究热点之一.过渡金属催化苯并咪唑的合成方法具有简单、直接、高效等优点,近年来发展迅速,寻找更简单、高效、廉价、环保的催化体系,一直是化学工作者研究的目标.本文综述了当前报道较多的几种过渡金属催化合成苯并咪唑新方法的研究进展,并简要介绍了各类催化体系的优缺点.     

β-酮砜的合成进展(2012-2022)

β-酮砜是一类重要的含硫化合物和有机合成中间体,广泛用于构建天然产物和各种重要的有机化合物.目前已开发了多种方法来合成目标化合物,并成功应用于一些有价值的合成转化.本文从过渡金属催化、非金属催化、光介导以及电催化4个方面重点概述了近十年来β-酮砜的合成进展.其中,以亚磺酸盐和磺酰肼等为砜基源的研究报导较多,构筑β-酮砜类化合物反应已经从传统的过渡金属催化发展到光或者电化学的催化合成.     

过渡金属催化1,2,4-三唑衍生物的合成研究进展

1,2,4-三唑衍生物在医药、农药、功能性材料等多领域应用广泛,该类化合物的合成也成为当前的热点之一,尤其是过渡金属催化1,2,4-三唑的合成具有简单、直接、高效等优点,近年来发展迅速.本文针对当前报道较多的几种过渡金属催化1,2,4-三唑合成新方法的研究进展进行了简要介绍.     

铁、钴、铜酞菁催化2-氨基苯甲醇氧化制备喹唑啉和喹啉（英文）

酞菁金属络合物在空气中催化2-氨基苄醇与腈和酮的氧化缩合反应,分别制得喹唑啉和喹啉.经过系统研究发现,铁(II)酞菁在喹唑啉合成中显示出较高的催化活性,而铜(II)酞菁在喹啉制备中显示出较高的催化活性.在优化的条件下,各种腈和酮具有良好的适应性,从而以高收率得到相应的产物.     

新型喹唑啉酮衍生物的合成

以醛、 丙二腈和酮为起始原料, 在乙酸铵的催化下一锅合成了2,6-二氰基苯胺衍生物3, 化合物3在NaOH催化下, 与酮经过分子内Pinner反应到Dimroth重排组合转化, 得到新型多取代喹唑啉酮衍生物5. 化合物5的结构经IR, ¹H NMR, ¹³C NMR和MS表征. 喹唑啉酮衍生物是一系列药物的重要中间体.     

由α-氰基二硫缩烯酮制备多取代喹唑啉酮化合物

以α-氰基乙酸甲酯为起始原料,经与二硫化碳、碘甲烷反应先得到α-氰基二硫缩烯酮1,1与苯乙酮2反应得2H-吡喃-2-酮-3-腈化物3,碱诱导下3再与丙二腈经环转化得到多取代邻氨基芳香腈4,4与酮5在氢氧化钠催化下环化得到多取代喹唑啉酮目标物6.这组连续转化合成多取代喹唑啉酮的反应具有原料简便、反应温和等优点.     

过渡金属催化的酮羰基导向C—H键官能化反应进展

近二十年来,过渡金属催化的酮羰基导向C—H键活化已发展成为在酮的非传统反应位点构建碳碳键和碳杂键(杂原子为氮、氟和氧原子等)的强有力而快捷的手段.其中,钌、铑、钯、铱等贵金属催化的酮羰基导向C—H键活化反应得到了广泛研究,而廉价3d金属锰、铁和钴催化的酮羰基导向C—H活化反应逐渐成为当前研究的热点.文中按照过渡金属催化的酮羰基导向C—H键官能化的不同反应类型(烷基化、烯基化、酰胺化、芳基化、环化等)综述了该领域近年来(2014～2021)的研究进展.     

喹唑啉稠合螺杂环化合物的合成及晶体结构

许多螺杂环化合物及喹唑啉化合物具有抗癌、消炎、抗真菌、抗细菌、抗结核、抗肿瘤以及除草等生物活性,将噻唑酮和喹唑啉稠合环结构与螺杂环结构合为一体,合成新的喹唑啉稠合螺杂环化合物,以期得到具有更高生物活性的化合物,是当前化学家研究的课题之一,1,3-偶极环加成反应是合成五元杂环的常用方法,采用环外双键结构的化合物为亲偶极体,     

碘催化下离子液体中2-苯基-2-苯甲酰基喹唑啉衍生物的合成

介绍了一种以离子液体为绿色介质合成2,3-二氢化-2-苯基-2-苯甲酰基喹唑啉-4-酮衍生物的方法.该方法是碘催化下的2-氨基苯甲酰胺和二苯基乙二酮反应,产物2,3-二氢化-2-苯基-2-苯甲酰基-3-苯乙基喹唑啉-4-酮(3f)的结构通过X射线衍射分析确证.     

可见光诱导的2-(苄基氨基)苯甲酰胺合成4(3H)-喹唑啉酮（英文）

发展了一种环境友好的可见光诱导的反应.该方法在简单、温和的反应条件下可以通过2-(苄基氨基)苯甲酰胺来高效合成4(3H)-喹唑啉酮化合物.不使用任何金属、光催化剂和其他添加剂,仅在室温下用blueLED照射,反应就可以顺利进行并高收率得到相应的喹唑啉酮化合物.该反应具有反应底物范围广、官能团兼容性好、操作简单等优点,同时可进行克级反应.机理研究表明,该反应经历自由基历程.     

The Synthesis of Quinazolinones from Olefins,CO, and Amines over a Heterogeneous Ru‐clusters/Ceria Catalyst

Quinazolinones, an important class of heterocyclic compounds, have been widely used in pharmaceuticals because of their biological activity. However, the efficient and economical synthesis of quinazolinones has remained a challenge. A novel synthetic approach has now been developed to produce quinazolinones from olefins, CO, and amines over heterogeneous Ru‐clusters/ceria catalyst in the absence of acids, bases, and oxidants. Furthermore, H₂O is generated as the only by‐product. A series of quinazolinones with aromatic or non‐aromatic substituents can be obtained in yields of up to 99 %. The Ru‐clusters/ceria can be reused at least four times. The analysis of the E‐factor (environmental impact factor) for the synthesis of 2‐ethyl quinazolinone suggests that this system is more environmentally friendly than other processes reported previously.     

The Synthesis of Quinazolinones from Olefins,CO, and Amines over a Heterogeneous Ru‐clusters/Ceria Catalyst

Quinazolinones, an important class of heterocyclic compounds, have been widely used in pharmaceuticals because of their biological activity. However, the efficient and economical synthesis of quinazolinones has remained a challenge. A novel synthetic approach has now been developed to produce quinazolinones from olefins, CO, and amines over heterogeneous Ru‐clusters/ceria catalyst in the absence of acids, bases, and oxidants. Furthermore, H₂O is generated as the only by‐product. A series of quinazolinones with aromatic or non‐aromatic substituents can be obtained in yields of up to 99 %. The Ru‐clusters/ceria can be reused at least four times. The analysis of the E‐factor (environmental impact factor) for the synthesis of 2‐ethyl quinazolinone suggests that this system is more environmentally friendly than other processes reported previously.     

Y(OTf)3-catalyzed heterocyclic formation via aerobic oxygenation: An approach to dihydro quinazolinones and quinazolinones

The Y(OTf)₃-catalyzed aerobic oxidative cyclization reaction for the selective synthesis of dihydroquinazolinones and quinazolinones has been developed. This method provides a practical, effective and green synthetic approach to dihydroquinazolinones and quinazolinones which both are important units in many biologically active compounds.     

Imides: forgotten players in the Ugi reaction. One-pot multicomponent synthesis of quinazolinones

Up to now, the synthesis of quinazolinones has required lengthy synthetic procedures. Here, we describe an innovative one-pot multicomponent reaction leading to highly substituted quinazolinones. We believe that this novel transformation may open the door for the generation of new and pharmacologically active quinazolinones, but, most important of all, the resurrection of the imide-Ugi scaffold paves the way for the synthesis of novel molecular architectures.     

Remarkably flexible quinazolinones—synthesis and biological applications

Even though several quinazolinone derivatives have been synthesized, still there is a constant demand for designing and synthesis of new quinazolinone derivatives by fine-tuning the electronic and steric properties of substituents due to their interesting structure-based biological utilities and the versatile chemistry. While many of the synthetic routes are useful as building blocks in synthetic organic chemistry, the drawbacks of some of these methods like unsatisfactory or variable yields, prolonged reaction times, inadequate tolerance to other substrates, including the use of costly catalysts/reagents. This review article is mainly focused on various synthetic routes for the preparation of quinazolinones, their important properties and applications.     

Microwave-assisted synthesis of bioactive quinazolines and quinazolinones

This paper aims to review recent developments in the synthesis of quinazolines and quinazolinone derivatives under conditions that include the application of microwave heating in the ring forming step. Recently, two reviews on the synthesis and chemistry of natural and synthetic quinazolines and quinazolinones have been published. This review highlights significant examples where microwave heating has been either synthetically enabling or has provided a key advantage over conventional thermal methods. Wherever possible, this review will focus on chemistry carried out using monomode systems and well-designed type of instrumentation. The review is grouped according to the main heterocycle types in order of increasing complexity; commencing with quinazolines and their derivatives. The microwave-assisted synthesis of quinazolines and quinazolinones will be classified and based on the substitution patterns of the ring system. Syntheses of heterocyclic systems of particular biological or commercial interest are emphasized.     

Ligand-free palladium assisted insertion of isocyanides to urea derivatives for cascade synthesis of phenylamino-substituted quinazolinones

Palladium catalyzed cascade coupling of substituted urea derivatives and tert-butyl isocyanide for the efficient synthesis of phenylamino-substituted quinazolinones has been developed in moderate to good yields. This method provides a short and alternative approach for the synthesis of quinazolinones derivatives which are valuable compounds with biological and pharmacological potentials. A plausible mechanistic scheme is proposed.     

A New Route to 4-Phenyl-2(1H) Quinazolinones; Reactions of 2-Amino Benzophenones with Chlorosulfonyl Isocyanate

Abstract

We have been interested in the synthesis of substituted quinazolinones as a part of our continuing research programme in search of potent physiologically active molecules. The present communication explores further synthetic uses of chlorosulfonyl isocyanate (CSI), a reagent developed by Graf^1,2 and extensively employed in the preparation of a wide variety of heterocyclic systems as well in various synthetic conversions³.     

Palladium‐Catalyzed Carbonylative Difunctionalization of C=N Bond of Azaarenes or Imines to Quinazolinones

Supporting information for this article is given via a link at the end of the document. By intercepting the acylpalladium species with C=N bond of azaarenes or imines other than free amines or alcohols, the difunctionalization of C=N bond was established via palladium‐catalyzed carbonylation/nucleophilic addition sequence. This method is compatible with a diverse range of azaarenes and imines and allows for the efficient synthesis of a wide range of quinazolinones and derivatives. The synthetic utility has been demonstrated by one‐step synthesis of evodiamine and its analogue with inexpensive starting materials.     

Multicomponent reaction of benzyl halides: Synthesis of [1,2,4]triazolo/benzimidazolo quinazolinones

We demonstrated a simple, highly efficient, one-pot method to construct triazolo/benzimidazolo quinazolinones through a cascade of oxidation, Knoevenagel condensation, and Michael addition followed by cyclization and dehydration. This protocol tolerates easily available benzyl halides, 2-amino benzimidazole/3-amino-1,2,4-triazole, and α-hydroxy C-H acids as starting materials using trimethyl amine N-oxide in ethanol. To the best of our knowledge, this is the first example of synthesis of triazolo/benzimidazolo quinazolinones directly from benzyl halides in one pot. Simple procedure, environmental friendliness, mild reaction conditions, and good yields are the attractive features of this method.