The main achievements and development trends of the past 10–15 years related to the catalytic cyclopropanation of unsaturated compounds with diazomethane are integrated and analyzed. The attention is focused on the most efficient catalysts based on palladium compounds. Data on the effects of substrate structure and nature of catalyst components on the regio- and stereoselectivity of these reactions are systematized. Characteristic features of safe methods for diazomethane generation are considered, including the use of membrane technologies and continuous-flow and in situ preparation methods, which have prospects for industrial application. The bibliography includes 281 references.
{"title":"Recent advances in the catalytic cyclopropanation of unsaturated compounds with diazomethane","authors":"L. Menchikov, E. V. Shulishov, Yu. V. Tomilov","doi":"10.1070/RCR4982","DOIUrl":"https://doi.org/10.1070/RCR4982","url":null,"abstract":"The main achievements and development trends of the past 10–15 years related to the catalytic cyclopropanation of unsaturated compounds with diazomethane are integrated and analyzed. The attention is focused on the most efficient catalysts based on palladium compounds. Data on the effects of substrate structure and nature of catalyst components on the regio- and stereoselectivity of these reactions are systematized. Characteristic features of safe methods for diazomethane generation are considered, including the use of membrane technologies and continuous-flow and in situ preparation methods, which have prospects for industrial application. The bibliography includes 281 references.","PeriodicalId":21523,"journal":{"name":"Russian Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":7.7,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"59008965","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The review considers the research and engineering works in selected fields of the physical chemistry of gas hydrates and gas hydrate technologies, mainly performed over the last 10–15 years. Data on the hydrate structures are given, including the structures formed during phase transitions at low temperatures, and on new hydrate structures that are formed under ultrahigh pressures. The dynamics of guest and host subsystems is considered in brief. Phase diagrams of systems involving hydrate formation (in particular, in some porous media) and methods for calculating phase equilibria and compositions of hydrates in these systems are analyzed. Data on the hydrates formed by ‘non-classical’ hydrate formers (alcohols, amines, ammonia, etc.) studied in the last decade and on some of their properties are presented. The Section devoted to hydrate formation kinetics addresses the effect of compounds dissolved in water (surfactants, low-dosage inhibitors) and catalysts on this process. The hydrate growth dynamics on the water surface and hydrate decomposition-formation processes in disperse systems are discussed. Among technological applications, the attention is focused on gas storage and transportation in the hydrate form. Methods for the preparation of hydrates are considered. The bibliography includes 618 references.
{"title":"Physical chemistry and technological applications of gas hydrates: topical aspects","authors":"A. Manakov, A. Stoporev","doi":"10.1070/RCR4986","DOIUrl":"https://doi.org/10.1070/RCR4986","url":null,"abstract":"The review considers the research and engineering works in selected fields of the physical chemistry of gas hydrates and gas hydrate technologies, mainly performed over the last 10–15 years. Data on the hydrate structures are given, including the structures formed during phase transitions at low temperatures, and on new hydrate structures that are formed under ultrahigh pressures. The dynamics of guest and host subsystems is considered in brief. Phase diagrams of systems involving hydrate formation (in particular, in some porous media) and methods for calculating phase equilibria and compositions of hydrates in these systems are analyzed. Data on the hydrates formed by ‘non-classical’ hydrate formers (alcohols, amines, ammonia, etc.) studied in the last decade and on some of their properties are presented. The Section devoted to hydrate formation kinetics addresses the effect of compounds dissolved in water (surfactants, low-dosage inhibitors) and catalysts on this process. The hydrate growth dynamics on the water surface and hydrate decomposition-formation processes in disperse systems are discussed. Among technological applications, the attention is focused on gas storage and transportation in the hydrate form. Methods for the preparation of hydrates are considered. The bibliography includes 618 references.","PeriodicalId":21523,"journal":{"name":"Russian Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":7.7,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"59009395","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Many paramagnetic metal complexes have emerged as unique magnetic materials (single-molecule magnets), which behave as conventional magnets at the single-molecule level, thereby making it possible to use them in modern devices for data storage and processing. The rational design of these complexes, however, requires a deep understanding of the physical laws behind a single-molecule magnet behaviour, the mechanisms of magnetic relaxation that determines the magnetic properties and the relationship of these properties with the structure of single-molecule magnets. This review focuses on the physical methods providing such understanding, including different versions and various combinations of magnetometry, electron paramagnetic and nuclear magnetic resonance spectroscopy, optical spectroscopy and X-ray diffraction. Many of these methods are traditionally used to determine the composition and structure of new chemical compounds. However, they are rarely applied to study molecular magnetism. The bibliography includes 224 references.
{"title":"Modern physical methods for the molecular design of single-molecule magnets","authors":"V. Novikov, Y. Nelyubina","doi":"10.1070/RCR5002","DOIUrl":"https://doi.org/10.1070/RCR5002","url":null,"abstract":"Many paramagnetic metal complexes have emerged as unique magnetic materials (single-molecule magnets), which behave as conventional magnets at the single-molecule level, thereby making it possible to use them in modern devices for data storage and processing. The rational design of these complexes, however, requires a deep understanding of the physical laws behind a single-molecule magnet behaviour, the mechanisms of magnetic relaxation that determines the magnetic properties and the relationship of these properties with the structure of single-molecule magnets. This review focuses on the physical methods providing such understanding, including different versions and various combinations of magnetometry, electron paramagnetic and nuclear magnetic resonance spectroscopy, optical spectroscopy and X-ray diffraction. Many of these methods are traditionally used to determine the composition and structure of new chemical compounds. However, they are rarely applied to study molecular magnetism. The bibliography includes 224 references.","PeriodicalId":21523,"journal":{"name":"Russian Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":7.7,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"59009785","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Analogues and derivatives of nucleic acid components have been used as key drugs in different areas of medicine over the past decades. The replacement of one or more nitrogen atoms of the heterocyclic base with a CH group affords deazapurine nucleoside analogues, and the replacement of the methine group with a nitrogen atom gives azapurine derivatives. A combination of aza and deaza moieties in the purine base leads to aza(deaza)-modified bases. Some nucleoside analogues were found to exhibit pronounced anticancer and antiviral activity. The synthesis and evaluation of biological activity of aza- and deazapurine nucleoside analogues have attracted interest from researchers four decades ago. This review describes and integrates the studies concerning certain aspects of the synthesis and(or) activity of various representatives of this class of compounds. The structure–biological activity relationships are analyzed. The successful approaches to the design of aza- and deazapurine nucleoside analogues are considered. A comparison is given for the methods of chemical and enzymatic synthesis of these compounds. The bibliography includes 161 references.
{"title":"Synthesis and biological activity of aza and deaza analogues of purine nucleosides","authors":"E. Matyugina, S. Kochetkov, A. Khandazhinskaya","doi":"10.1070/RCR5013","DOIUrl":"https://doi.org/10.1070/RCR5013","url":null,"abstract":"Analogues and derivatives of nucleic acid components have been used as key drugs in different areas of medicine over the past decades. The replacement of one or more nitrogen atoms of the heterocyclic base with a CH group affords deazapurine nucleoside analogues, and the replacement of the methine group with a nitrogen atom gives azapurine derivatives. A combination of aza and deaza moieties in the purine base leads to aza(deaza)-modified bases. Some nucleoside analogues were found to exhibit pronounced anticancer and antiviral activity. The synthesis and evaluation of biological activity of aza- and deazapurine nucleoside analogues have attracted interest from researchers four decades ago. This review describes and integrates the studies concerning certain aspects of the synthesis and(or) activity of various representatives of this class of compounds. The structure–biological activity relationships are analyzed. The successful approaches to the design of aza- and deazapurine nucleoside analogues are considered. A comparison is given for the methods of chemical and enzymatic synthesis of these compounds. The bibliography includes 161 references.","PeriodicalId":21523,"journal":{"name":"Russian Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":7.7,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"59010654","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pickering emulsions are emulsions that are stabilized by solid micro- and nanoparticles. These emulsions are in most demand for applications where the use of surfactants is restricted. The review addresses stabilization of Pickering emulsions. The attention is focused on the flocculation, coalescence, sedimentation and Ostwald ripening processes taking place in these emulsions. The structures formed by particles in the emulsion dispersion medium and in thin interlayers between the dispersed phase droplets are analyzed. Methods for preparing colloidosomes, that is, microcapsules of assembled particles, from Pickering emulsions are considered. Colloidosomes are promising for the encapsulation and prolonged release of active substances. Conversely, Pickering stimuli-responsive emulsions provide intense release of encapsulated substances upon the change in the environmental parameters. This can be used not only in medicine and pharmacology, but also in sensors, food industry, paint and varnish industry, petroleum production, etc. The bibliography includes 340 references.
{"title":"Pickering emulsions: structure, properties and the use as colloidosomes and stimuli-responsive emulsions","authors":"M. Koroleva, E. Yurtov","doi":"10.1070/RCR5024","DOIUrl":"https://doi.org/10.1070/RCR5024","url":null,"abstract":"Pickering emulsions are emulsions that are stabilized by solid micro- and nanoparticles. These emulsions are in most demand for applications where the use of surfactants is restricted. The review addresses stabilization of Pickering emulsions. The attention is focused on the flocculation, coalescence, sedimentation and Ostwald ripening processes taking place in these emulsions. The structures formed by particles in the emulsion dispersion medium and in thin interlayers between the dispersed phase droplets are analyzed. Methods for preparing colloidosomes, that is, microcapsules of assembled particles, from Pickering emulsions are considered. Colloidosomes are promising for the encapsulation and prolonged release of active substances. Conversely, Pickering stimuli-responsive emulsions provide intense release of encapsulated substances upon the change in the environmental parameters. This can be used not only in medicine and pharmacology, but also in sensors, food industry, paint and varnish industry, petroleum production, etc. The bibliography includes 340 references.","PeriodicalId":21523,"journal":{"name":"Russian Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":7.7,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"59010960","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ionic liquids (ILs) are considered as an alternative to conventional organic solvents used in industry, and the distinctive physical and chemical properties of these substances are being actively investigated. Ionic liquids can be applied in a number of areas, including polymerization reactions, catalysis and biomedicine. Although the overwhelming majority of studies are focused on the liquid state of ILs, an understanding of their properties in a glassy state can stimulate innovations in organic synthesis, energy storage and cryopreservation. This review aims at a systematic description of the properties and applications of ILs in the glassy state, which has not been published previously and appears relevant and demanded by the scientific community. The bibliography includes 286 references.
{"title":"Ionic liquid glasses: properties and applications","authors":"M. Ivanov, N. Surovtsev, M. Fedin","doi":"10.1070/RCR5031","DOIUrl":"https://doi.org/10.1070/RCR5031","url":null,"abstract":"Ionic liquids (ILs) are considered as an alternative to conventional organic solvents used in industry, and the distinctive physical and chemical properties of these substances are being actively investigated. Ionic liquids can be applied in a number of areas, including polymerization reactions, catalysis and biomedicine. Although the overwhelming majority of studies are focused on the liquid state of ILs, an understanding of their properties in a glassy state can stimulate innovations in organic synthesis, energy storage and cryopreservation. This review aims at a systematic description of the properties and applications of ILs in the glassy state, which has not been published previously and appears relevant and demanded by the scientific community. The bibliography includes 286 references.","PeriodicalId":21523,"journal":{"name":"Russian Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":7.7,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"59011034","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Dmitry I. Bugaenko, A. Volkov, A. Karchava, M. Yurovskaya
Arylation methods based on the generation and use of aryl radicals have been a rapidly growing field of research in recent years and currently represent a powerful strategy for carbon – carbon and carbon – heteroatom bond formation. The progress in this field is related to advances in the methods for generation of aryl radicals. The currently used aryl radical precursors include aryl halides, aryldiazonium and diaryliodonium salts, arylcarboxylic acids and their derivatives, arylboronic acids, arylhydrazines, organosulfur(II, VI) compounds and some other compounds. Aryl radicals are generated under mild conditions by single electron reduction or oxidation of precursors induced by conventional reagents, visible light or electric current. A crucial role in the development of the radical arylation methodology belongs to photoredox processes either catalyzed by transition metal complexes or organic dyes or proceeding without catalysts. Unlike the conventional transition metal-catalyzed arylation methods, radical arylation reactions proceed very often at room temperature and have high functional group tolerance. Without claiming to be exhaustive, this review covers the most important advances of the current decade in the generation and synthetic applications of (het)aryl radicals. Examples of reactions are given and mechanistic insights are highlighted. The bibliography includes 341 references.
{"title":"Generation of aryl radicals by redox processes. Recent progress in the arylation methodology","authors":"Dmitry I. Bugaenko, A. Volkov, A. Karchava, M. Yurovskaya","doi":"10.1070/RCR4959","DOIUrl":"https://doi.org/10.1070/RCR4959","url":null,"abstract":"Arylation methods based on the generation and use of aryl radicals have been a rapidly growing field of research in recent years and currently represent a powerful strategy for carbon – carbon and carbon – heteroatom bond formation. The progress in this field is related to advances in the methods for generation of aryl radicals. The currently used aryl radical precursors include aryl halides, aryldiazonium and diaryliodonium salts, arylcarboxylic acids and their derivatives, arylboronic acids, arylhydrazines, organosulfur(II, VI) compounds and some other compounds. Aryl radicals are generated under mild conditions by single electron reduction or oxidation of precursors induced by conventional reagents, visible light or electric current. A crucial role in the development of the radical arylation methodology belongs to photoredox processes either catalyzed by transition metal complexes or organic dyes or proceeding without catalysts. Unlike the conventional transition metal-catalyzed arylation methods, radical arylation reactions proceed very often at room temperature and have high functional group tolerance. Without claiming to be exhaustive, this review covers the most important advances of the current decade in the generation and synthetic applications of (het)aryl radicals. Examples of reactions are given and mechanistic insights are highlighted. The bibliography includes 341 references.","PeriodicalId":21523,"journal":{"name":"Russian Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":7.7,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"59008495","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A. Akulov, M. Varaksin, V. Charushin, O. Chupakhin
This is the first systematic review of the most relevant approaches to direct C(sp2)–H bond functionalization of azomethine derivatives. The scope of the applicability of various transformations is analyzed. The review assesses prospects of the application of this functionalization strategy in the multistep synthesis of valuable compounds for use in medicinal chemistry, materials science and related areas. The bibliography includes 124 references.
{"title":"C(sp2) – H functionalization of aldimines and related compounds: advances and prospects","authors":"A. Akulov, M. Varaksin, V. Charushin, O. Chupakhin","doi":"10.1070/RCR4978","DOIUrl":"https://doi.org/10.1070/RCR4978","url":null,"abstract":"This is the first systematic review of the most relevant approaches to direct C(sp2)–H bond functionalization of azomethine derivatives. The scope of the applicability of various transformations is analyzed. The review assesses prospects of the application of this functionalization strategy in the multistep synthesis of valuable compounds for use in medicinal chemistry, materials science and related areas. The bibliography includes 124 references.","PeriodicalId":21523,"journal":{"name":"Russian Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":7.7,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"59008778","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The review is devoted to extraction solvents of new generation, so called combined solvents, which include ionic liquids, aqueous biphasic systems and eutectic solvents. Most of modern combined solvents are based on organic ionic components. These solvents are associated with high expectations as they are able to provide the environmental safety and green character of extraction, which are priority tasks for the development of chemistry and chemical engineering. For all classes, an overview and a brief history of research are presented; details of structure and properties are discussed; various extraction systems are compared; and typical examples of extraction of metal ions and organic compounds are given. The lack of uniform terminology and difficulties in interpreting the behaviour of some systems, especially eutectic solvents, are outlined. The advantages and drawbacks of new generation extraction solvents and relevant research tasks are summarized. The bibliography includes 408 references.
{"title":"New generation extraction solvents: from ionic liquids and aqueous biphasic systems to deep eutectic solvents","authors":"I. Pletnev, S. Smirnova, A. V. Sharov, Y. Zolotov","doi":"10.1070/RCR5007","DOIUrl":"https://doi.org/10.1070/RCR5007","url":null,"abstract":"The review is devoted to extraction solvents of new generation, so called combined solvents, which include ionic liquids, aqueous biphasic systems and eutectic solvents. Most of modern combined solvents are based on organic ionic components. These solvents are associated with high expectations as they are able to provide the environmental safety and green character of extraction, which are priority tasks for the development of chemistry and chemical engineering. For all classes, an overview and a brief history of research are presented; details of structure and properties are discussed; various extraction systems are compared; and typical examples of extraction of metal ions and organic compounds are given. The lack of uniform terminology and difficulties in interpreting the behaviour of some systems, especially eutectic solvents, are outlined. The advantages and drawbacks of new generation extraction solvents and relevant research tasks are summarized. The bibliography includes 408 references.","PeriodicalId":21523,"journal":{"name":"Russian Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":7.7,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"59009729","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The review summarizes the current knowledge about heterogeneous semiconductor photocatalysts that are active towards photocatalytic reduction of carbon dioxide and molecular nitrogen under visible and near-UV light. The main classes of these photocatalysts and characteristic features of their application in the target processes are considered. Primary attention is given to photocatalysts based on titanium dioxide, which have high activity and stability in the carbon dioxide reduction. For the first time, the photofixation of nitrogen under irradiation in the presence of various semiconductor materials is considered in detail. The bibliography includes 264 references.
{"title":"Semiconductor photocatalysts and mechanisms of carbon dioxide reduction and nitrogen fixation under UV and visible light","authors":"E. Kozlova, M. Lyulyukin, D. Kozlov, V. Parmon","doi":"10.1070/RCR5004","DOIUrl":"https://doi.org/10.1070/RCR5004","url":null,"abstract":"The review summarizes the current knowledge about heterogeneous semiconductor photocatalysts that are active towards photocatalytic reduction of carbon dioxide and molecular nitrogen under visible and near-UV light. The main classes of these photocatalysts and characteristic features of their application in the target processes are considered. Primary attention is given to photocatalysts based on titanium dioxide, which have high activity and stability in the carbon dioxide reduction. For the first time, the photofixation of nitrogen under irradiation in the presence of various semiconductor materials is considered in detail. The bibliography includes 264 references.","PeriodicalId":21523,"journal":{"name":"Russian Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":7.7,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"59009854","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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