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Preliminary modelling as the first stage of targeted organic synthesis 作为目标有机合成第一阶段的初步建模
IF 7.7 2区 化学 Q1 Chemistry Pub Date : 2021-08-01 DOI: 10.1070/RCR5012
I. Titov, V. S. Stroylov, P. Rusina, I. Svitanko
The review aims to present a classification and applicability analysis of methods for preliminary molecular modelling for targeted organic, catalytic and biocatalytic synthesis. The following three main approaches are considered as a primary classification of the methods: modelling of the target – ligand coordination without structural information on both the target and the resulting complex; calculations based on experimentally obtained structural information about the target; and dynamic simulation of the target – ligand complex and the reaction mechanism with calculation of the free energy of the reaction. The review is meant for synthetic chemists to be used as a guide for building an algorithm for preliminary modelling and synthesis of structures with specified properties. The bibliography includes 353 references.
本文综述了针对有机、催化和生物催化合成的初步分子建模方法的分类和适用性分析。以下三种主要方法被认为是方法的主要分类:在没有目标和所得复合物的结构信息的情况下对目标-配体配位进行建模;根据实验得到的目标结构信息进行计算;并对靶配体配合物进行了动态模拟,对反应机理进行了计算,计算了反应的自由能。该综述旨在为合成化学家提供指导,用于构建具有特定性质的结构的初步建模和合成算法。参考书目包括353篇参考文献。
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引用次数: 1
Hydrogen energy: development prospects and materials 氢能:发展前景及材料
IF 7.7 2区 化学 Q1 Chemistry Pub Date : 2021-06-01 DOI: 10.1070/RCR5014
S. Filippov, A. Yaroslavtsev
The review addresses the prospects of global hydrogen energy development. Particular attention is given to the design of materials for sustainable hydrogen energy applications, including hydrogen production, purification, storage, and conversion to energy. The review highlights the key role of oxide-supported metal or alloy nanoparticles as catalysts in the hydrogen production via the conversion of natural gas or alcohols. An alternative approach is the pyrolysis of hydrocarbons giving hydrogen and carbon. The direct production of high-purity hydrogen can be performed using electrolysis or membrane catalysis. Apart from conventional hydrogen storage methods such as the compression and liquefaction, the hydrogen alloy absorption and chemical conversion to liquid carriers (ammonia and toluene cycles) are considered. Fuel cells, containing catalysts and proton-conducting membranes as the key components, are used for hydrogen energy generation. Binary platinum alloys or core – shell structures supported on carbon or oxides can be employed to facilitate the oxygen electroreduction and CO electrooxidation in low-temperature fuel cells. High conductivity and selectivity are provided by perfluorinated sulfonic acid membranes. The high cost of the latter materials dictates the development of alternative membrane materials. A crucial issue in high-temperature fuel cells is the necessity of reducing the operating temperature and ohmic losses. This problem can be solved by designing thin-film materials and replacing oxygen-conducting ceramic membranes by proton-conducting membranes. The bibliography includes 290 references.
综述了全球氢能发展的前景。特别关注可持续氢能源应用的材料设计,包括氢的生产,净化,储存和转化为能源。该综述强调了氧化物负载的金属或合金纳米颗粒作为催化剂在天然气或醇转化制氢中的关键作用。另一种方法是碳氢化合物的热解产生氢和碳。直接生产高纯度氢可以通过电解或膜催化进行。除压缩和液化等传统储氢方法外,还考虑了氢合金的吸收和化学转化为液体载体(氨和甲苯循环)。燃料电池以催化剂和质子导电膜为关键部件,用于氢能源的生产。以碳或氧化物为载体的二元铂合金或核壳结构可用于低温燃料电池中的氧电还原和CO电氧化。全氟磺酸膜具有高导电性和选择性。后一种材料的高成本决定了替代膜材料的发展。高温燃料电池的一个关键问题是必须降低工作温度和欧姆损耗。这一问题可以通过设计薄膜材料和用质子导电膜代替氧导电陶瓷膜来解决。参考书目包括290篇参考文献。
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引用次数: 63
Furan monomers and polymers from renewable plant biomass 可再生植物生物质中的呋喃单体和聚合物
IF 7.7 2区 化学 Q1 Chemistry Pub Date : 2021-06-01 DOI: 10.1070/RCR5018
V. Kashparova, Daria V. Chernysheva, V. Klushin, Veronika E. Andreeva, O. A. Kravchenko, N. Smirnova
Plant biomass is considered the main source of renewable carbon raw materials, which is a viable alternative to crude oil and natural gas and provides compounds with a low carbon footprint. The most promising direction for the conversion of biomass is the synthesis of 5-hydroxymethylfurfural, which is regarded as a platform chemical, the basis for the synthesis of valuable compounds, including monomers and polymers. The move of the polymer industry to renewable plant materials will contribute to solving global environmental problems and ensure the sustainability and environmental safety of plastics production. This review analyzes recent advances in the preparation of key C6-furan platform chemicals, such as 5-hydroxymethylfurfural, 2,5-furandicarboxylic acid, 2,5-diformylfuran, 2,5-bis(hydroxymethyl)furan, levulinic acid, and their use for the production of monomers and polymers based on renewable plant biomass. Production processes of widely known furan polyesters and polyamides, such as polyethylene-, polypropylene-, polybutylene furanoates, polyhexamethylene furanamide, are considered, as well as developments towards novel promising materials that are furan copolymers and polymer mixtures. For the first time, studies have been systematized aimed at converting liquid and solid wastes of the synthesis of platform chemicals, known as humins, into a range of value-added products, including organic compounds, porous carbon materials, thermosetting binders, and anticorrosive coatings that can replace similar materials based on fossil raw materials. Economic and environmental prospects and problems of production and consumption of furan polymers are considered. The bibliography includes 275 references.
植物生物质被认为是可再生碳原料的主要来源,是原油和天然气的可行替代品,并提供低碳足迹的化合物。生物质转化最有希望的方向是合成5-羟甲基糠醛,它被认为是一种平台化学物质,是合成有价值化合物(包括单体和聚合物)的基础。聚合物工业向可再生植物材料的转变将有助于解决全球环境问题,确保塑料生产的可持续性和环境安全性。本文综述了5-羟甲基糠醛、2,5-呋喃二羧酸、2,5-二甲酰呋喃、2,5-双(羟甲基)呋喃、乙酰丙酸等主要c6 -呋喃平台化合物的制备及其在可再生植物生物质单体和聚合物生产中的应用进展。考虑了众所周知的呋喃聚酯和聚酰胺的生产工艺,如聚乙烯、聚丙烯、聚呋喃丁烯酸酯、聚六亚甲基呋喃酰胺,以及呋喃共聚物和聚合物混合物等有前途的新型材料的发展。这是第一次系统化的研究,旨在将合成平台化学品的液体和固体废物转化为一系列增值产品,包括有机化合物、多孔碳材料、热固性粘合剂和防腐涂料,这些产品可以取代基于化石原料的类似材料。讨论了呋喃聚合物生产和消费的经济和环境前景以及存在的问题。参考书目包括275篇参考文献。
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引用次数: 12
Computational NMR of natural products 天然产物的计算核磁共振
IF 7.7 2区 化学 Q1 Chemistry Pub Date : 2021-05-17 DOI: 10.1070/RCR5027
V. Semenov, L. Krivdin
This review generalizes diverse computational NMR studies of different natural products involving true alkaloids (indole, quinolizidine, pyrrolizidine, piperidine, indolizidine, quinoline, isoquinoline, indoloquinoline, and guanidine alkaloids), pseudoalkaloids (terpenes and steroids), quinones, lactones, lactams, flavonoids, and many others. The diverse computational protocols employed in each particular case are thoroughly discussed with a special emphasis on their structural and stereochemical applications. The bibliography includes 165 references.
本文综述了不同天然产物的计算核磁共振研究,包括真生物碱(吲哚、喹啉、吡咯利西啶、哌啶、吲哚利西啶、喹啉、异喹啉、吲哚喹啉和胍类生物碱)、假生物碱(萜烯和类固醇)、醌类、内酯类、内酰胺类、类黄酮等。在每个特定情况下采用的各种计算协议进行了深入讨论,特别强调了它们的结构和立体化学应用。参考书目包括165个参考文献。
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引用次数: 4
Nonstoichiometry, structure and properties of nanocrystalline oxides, carbides and sulfides 纳米晶氧化物、碳化物和硫化物的非化学计量学、结构和性质
IF 7.7 2区 化学 Q1 Chemistry Pub Date : 2021-05-01 DOI: 10.1070/RCR4967
A. Valeeva, A. Rempel, S. Rempel, S. Sadovnikov, A. Gusev
The results of recent experimental studies of the influence of the size of oxide, carbide and sulfide nanoparticles on changes in their nonstoichiometry are analyzed and generalized. In relation to intrinsically nonstoichiometric titanium oxides and niobium and vanadium carbides, on the one hand, and stoichiometric silver sulfides, on the other hand, it is shown that a decrease in the particle size to the nano scale has a strong impact on the chemical composition of nanocrystalline compounds, viz., it leads to the occurrence of or increase in nonstoichiometry. A conclusion is drawn that interplay between the particle size and nonstoichiometry is common to all solid nanocrystalline substances and should be taken into account in studies on the synthesis, structure and properties of these systems. The bibliography includes 260 references.
本文对近年来氧化物、碳化物和硫化物纳米颗粒尺寸对其非化学计量变化影响的实验研究结果进行了分析和概括。对于本质上非化学计量的氧化钛和铌钒碳化物,以及化学计量的硫化银,研究表明,颗粒尺寸减小到纳米尺度会对纳米晶化合物的化学组成产生强烈的影响,即导致非化学计量的发生或增加。得出结论:粒径与非化学计量的相互作用是所有固体纳米晶物质共同存在的,在研究这些体系的合成、结构和性能时应考虑到这些相互作用。参考书目包括260篇参考文献。
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引用次数: 4
Alkyl complexes of divalent lanthanides and heavy alkaline earth metals 二价镧系元素与重碱土金属的烷基配合物
IF 7.7 2区 化学 Q1 Chemistry Pub Date : 2021-05-01 DOI: 10.1070/RCR4992
D. Khristolyubov, D. Lyubov, A. Trifonov
The review presents data on the synthesis, structure, reactivity, and catalytic activity of alkyl derivatives of rare earth metals in the oxidation state +2 (Sm, Eu, Yb) and their analogues containing heavy alkaline earth metals (Ca, Sr, Ba). The synthetic aspects and structural features of this unique class of organometallic compounds, which contain highly reactive M–C bonds, including alkyl, α-silylmethyl, and also benzyl, diphenylmethyl, and triphenylmethyl derivatives are considered. The bibliography includes 157 references.
综述了稀土金属+2氧化态(Sm、Eu、Yb)的烷基衍生物及其含重碱土金属(Ca、Sr、Ba)的类似物的合成、结构、反应性和催化活性的研究进展。这类独特的有机金属化合物含有高活性的M-C键,包括烷基,α-硅基甲基,以及苯,二苯基甲基和三苯基甲基衍生物,其合成方面和结构特征被考虑。参考书目包括157篇参考文献。
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引用次数: 4
Progress in the medicinal chemistry of organoboron compounds 有机硼化合物的药物化学研究进展
IF 7.7 2区 化学 Q1 Chemistry Pub Date : 2021-04-01 DOI: 10.1070/RCR4977
A. Tevyashova, M. Chudinov
The review aims to draw attention to the latest advances in the organoboron chemistry and therapeutic use of organoboron compounds. The synthetic strategies towards boron-containing compounds with proven in vitro and/or in vivo biological activities, including derivatives of boronic acids, benzoxaboroles, benzoxaborines and benzodiazaborines, are summarized. Approaches to the synthesis of hybrid structures containing an organoboron moiety as one of the pharmacophores are considered, and the effect of this modification on the pharmacological activity of the initial molecules is analyzed. On the basis of analysis of the published data, the most promising areas of research in the field of organoboron compounds are identified, including the latest methods of synthesis, modification and design of effective therapeutic agents. The bibliography includes 246 references.
该综述旨在引起人们对有机硼化学和有机硼化合物治疗应用的最新进展的关注。综述了具有体外和/或体内生物活性的含硼化合物的合成策略,包括硼酸衍生物、苯并恶硼化物、苯并恶硼化物和苯并二氮硼化物。考虑了合成含有有机硼部分作为药效团之一的杂化结构的方法,并分析了这种修饰对初始分子药理学活性的影响。在分析已发表数据的基础上,确定了有机硼化合物领域最有前景的研究领域,包括有效治疗剂的最新合成、修饰和设计方法。参考书目包括246篇参考文献。
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引用次数: 11
Mono- and sesquiterpenes as a starting platform for the development of antiviral drugs 单萜类和倍半萜类作为开发抗病毒药物的起始平台
IF 7.7 2区 化学 Q1 Chemistry Pub Date : 2021-04-01 DOI: 10.1070/RCR4969
O. Yarovaya, N. Salakhutdinov
The revies focuses on low-molecular-weight plant metabolites (mono- and sesquiterpenes) exhibiting antiviral activity. Data on antiviral action of both essential oils and plant extracts and their components are provided. Structures of biologically active natural mono- and sesquiterpenoids as well as their derivatives showing a pronounced antiviral activity are presented. A special attention is given to the description of targets for antiviral therapy. The mechanisms of action of antiviral agents are considered. The bibliography includes 163 references.
本文综述了具有抗病毒活性的低分子植物代谢物(单萜类和倍半萜类)。提供了精油和植物提取物及其成分抗病毒作用的数据。介绍了具有生物活性的天然单萜类和倍半萜类及其衍生物的结构,它们具有明显的抗病毒活性。特别注意抗病毒治疗的靶标描述。讨论了抗病毒药物的作用机制。参考书目包括163篇参考文献。
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引用次数: 13
Cycloaddition reactions of o-quinone methides with polarized olefins 邻醌类化合物与极性烯烃的环加成反应
IF 7.7 2区 化学 Q1 Chemistry Pub Date : 2021-04-01 DOI: 10.1070/RCR4971
V. Osyanin, A. V. Lukashenko, D. Osipov
The review summarizes and systematizes the [4+2]-cycloaddition reactions of o-quinone methides with electron-rich and electron-deficient olefins. The electron-rich substrates include vinyl ethers, vinyl sulfides, enamines, enamides, enols, furans, benzofurans and indoles, while the electron-deficient substrates are esters of unsaturated carboxylic acids, vinyl azides and quinones. Reactions with push-pull and captodative olefins are also considered. The mechanisms of some reactions are presented. A separate part of the review addresses reactions of p-quinone methides containing an o-hydroxyphenyl substituent at the exocyclic carbon atom, which can isomerize to o-quinone methides. Much attention is paid to oligomerization of o-quinone methides, which proceeds in the absence of active dienophiles or nucleophiles. The bibliography includes 217 references.
综述了邻醌甲酰胺与富电子和缺电子烯烃的[4+2]-环加成反应,并使其系统化。富电子的底物包括乙烯基醚、乙烯基硫化物、烯胺、烯酰胺、烯醇、呋喃、苯并呋喃和吲哚,而缺电子的底物是不饱和羧酸的酯、乙烯基叠氮化物和醌。还考虑了与推拉和捕获烯烃的反应。介绍了一些反应的机理。综述的另一部分论述了在外环碳原子上含有邻羟基苯基取代基的对醌甲氧基的反应,该反应可以异构化为邻醌甲氧羰基。人们非常关注邻醌甲酰胺的低聚,这是在没有活性亲二烯或亲核试剂的情况下进行的。参考书目包括217篇参考文献。
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引用次数: 3
Synthesis and reactivity of 3-(1-alkynyl)chromones 3-(1-炔基)色酮的合成及其反应活性
IF 7.7 2区 化学 Q1 Chemistry Pub Date : 2021-04-01 DOI: 10.1070/RCR5008
V. Sosnovskikh
For the first time, the literature data on the methods of synthesis and reactivity of 3-(1-alkynyl)chromones are summarized and systematized. The main method for obtaining these compounds is the Sonogashira cross-coupling reaction of 3-halochromones with terminal acetylenes, and their most important chemical properties include the transformation into furans, reactions with dinucleophiles, ambiphilic [4+2]- and [4+3]-cyclizations, and also dimerization and mixed condensation of 2-methyl-3-(1-alkynyl)chromones due to the vinylogous methyl group. Except for the oxacyclization to furans, chemical transformations of 3-(1-alkynyl)chromones are accompanied by pyrone ring transformation, in which not only the carbonyl group but also the triple bond can participate. This significantly increases the synthetic value of these compounds and ensures the production of more complex heterocyclic systems based on them. The mechanisms of the reactions are discussed, the conditions for their implementation and the yields of the resulting products are indicated. The bibliography includes 80 references.
首次对3-(1-炔基)色酮的合成方法和反应活性的文献资料进行了总结和系统化。获得这些化合物的主要方法是3-卤代色酮与末端乙炔的Sonogashira交叉偶联反应,它们最重要的化学性质包括转化为呋喃、与双核的反应、两亲性[4+2]-和[4+3]-环化,以及2-甲基-3-(1-炔基)色酮由于乙烯基甲基的二聚和混合缩合。3-(1-炔基)色酮的化学转化除了氧杂环化为呋喃外,还伴随着焦酮环的转化,其中不仅羰基可以参与,双键也可以参与。这显著提高了这些化合物的合成价值,并确保了基于它们的更复杂的杂环系统的生产。讨论了反应的机理,指出了反应的实施条件和产物的产率。参考书目包括80篇参考文献。
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引用次数: 2
期刊
Russian Chemical Reviews
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