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Yu. N. Ogibin

Other affiliations: Russian Academy
Bio: Yu. N. Ogibin is an academic researcher from Russian Academy of Sciences. The author has contributed to research in topics: Radical & Alkyl. The author has an hindex of 9, co-authored 100 publications receiving 314 citations. Previous affiliations of Yu. N. Ogibin include Russian Academy.


Papers
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TL;DR: In this paper, the first stage of the reaction to 1-hydroxy-1-cyanoalkyl and 1-cyclohexyl radicals was shown to be competitive with the second stage.
Abstract: 1. Alkanal cyanohydrins (ACH) of general formula R(CH2)3CH(OH)CN are oxidized by the system S2O82−Ag+ to the acids R(CH2)3COOH and NCCHRCH2CH2COOH, indicating the competitive conversion of the ACH in the initial stage of the reaction to 1-hydroxy-1-cyanoalkyl and 1-cyanoalkoxyl radicals. 2. The oxidation of acetaldehyde cyanohydrin at 60° proceeds at approximately twice the rate of the oxidation of butanal, pentanal, isopentanal, and heptanal cyanohydrins, and approximately ten times as fast as that of tert-butanol.
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TL;DR: In this article, the reaction of dialkyl esters of maleic and fumaric acids with dibenzoyl peroxide catalyzed by cupric ions in solution of the dialkyls maleates and Fumarates leads to the formation of tetralin-1,2,3,4,4-tetracarboxylic acid in high yields.
Abstract: The reaction of dialkyl esters of maleic and fumaric acids with dibenzoyl peroxide catalyzed by cupric ions in solution of the dialkyl maleates and fumarates leads to the formation of tetraalkyl esters of tetralin-1,2,3,4-tetracarboxylic acid in high yields.
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TL;DR: The free radical addition of methyl acetoacetate to 1-hexene, initiated by di-tert-butyl peroxide, leads main ly to the formation of the methyl ester of α-acetoxyoctanoic acid as discussed by the authors.
Abstract: The free radical addition of methyl acetoacetate to 1-hexene, initiated by di-tert-butyl peroxide, leads main ly to the formation of the methyl ester of α-acetoxyoctanoic acid. Together with the latter, small amounts of the carbomethoxymethyl ester of octanoic acid and the heptyl ester of acetoacetic acid are formed.
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TL;DR: In this article, the relationship between the ability of these radicals to undergo oxidative cyclization to lactones and the number of methylene groups (n) and also the effect of copper ions on the oxidative cyclization process was investigated.
Abstract: 1. ω-Carboxyalkyl radicals HOOC(CH2)nCH2, where n=4–7, were generated by the oxidative decarboxylation of pentane-, hexane-, heptane-, and octanedicarboxylic acids at 60°C in aqueous solution by the action of Na2S2O8 in the presence of silver nitrate. The relation between the ability of these radicals to undergo oxidative cyclization to lactones and the number of methylene groups (n) and also the effect of copper ions on the oxidative cyclization process were investigated. 2. The main products from oxidative cyclization ofω-carboxyalkyl radicals in the absence of copper ions areγ-alkyl-γ-butyrolactones. In addition, alkanoic acids (84–95%) are formed as a result of abstraction of H atoms from the organic substrates by the radicals. 3. The main products from the oxidative cyclization of theω-carboxyalkyl radicals in the presence of copper ions areγ-alkyl-Δα,β-butenoiides.ω-Alkenoic acids (58–98%) are formed as a result of the oxidativeβ-deprotonation of the radicals by the action of Cu(II).

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TL;DR: Progress is described in the field of electroorganic synthesis, a process that can be accomplished more efficiently and purposefully using modern computational tools, and summarizes recent advances.
Abstract: Electroorganic synthesis has become an established, useful, and environmentally benign alternative to classic organic synthesis for the oxidation or the reduction of organic compounds. In this context, the use of redox mediators to achieve indirect processes is attaining increased significance, since it offers many advantages compared to a direct electrolysis. Kinetic inhibitions that are associated with the electron transfer at the electrode/electrolyte interface, for example, can be eliminated and higher or totally different selectivity can be achieved. In many cases, a mediated electron transfer can occur against a potential gradient, meaning that lower potentials are needed, reducing the probability of undesired side-reactions. In addition, the use of electron transfer mediators can help to avoid electrode passivation resulting from polymer film formation on the electrode surface. Although the principle of indirect electrolysis was established many years ago, new, exciting and useful developments continue to be made. In recent years, several new types of redox mediators have been designed and examined, a process that can be accomplished more efficiently and purposefully using modern computational tools. New protocols including, the development of double mediatory systems in biphasic media, enantioselective mediation and heterogeneous electrocatalysis using immobilized mediators have been established. Furthermore, the understanding of mediated electron transfer reaction mechanisms has advanced. This review describes progress in the field of electroorganic synthesis and summarizes recent advances.

1,146 citations

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TL;DR: In this Outlook, illustrative examples of electrochemical reactions in the context of the synthesis of complex molecules are highlighted, showcasing the intrinsic benefits of electro chemical reactions versus traditional reagent-based approaches.
Abstract: While preparative electrolysis of organic molecules has been an active area of research over the past century, modern synthetic chemists have generally been reluctant to adopt this technology. In fact, electrochemical methods possess many benefits over traditional reagent-based transformations, such as high functional group tolerance, mild conditions, and innate scalability and sustainability. In this Outlook we highlight illustrative examples of electrochemical reactions in the context of the synthesis of complex molecules, showcasing the intrinsic benefits of electrochemical reactions versus traditional reagent-based approaches. Our hope is that this field will soon see widespread adoption in the synthetic community.

674 citations

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TL;DR: This review provides an overview on the use of anodic electrochemical methods for expediting the development of carbon-hydrogen functionalization and carbon-nitrogen bond formation strategies and aims to provide inspiration for future synthetic applications in the field of electrosynthesis.
Abstract: Conventional methods for carrying out carbon–hydrogen functionalization and carbon–nitrogen bond formation are typically conducted at elevated temperatures, and rely on expensive catalysts as well as the use of stoichiometric, and perhaps toxic, oxidants. In this regard, electrochemical synthesis has recently been recognized as a sustainable and scalable strategy for the construction of challenging carbon–carbon and carbon–heteroatom bonds. Here, electrosynthesis has proven to be an environmentally benign, highly effective and versatile platform for achieving a wide range of nonclassical bond disconnections via generation of radical intermediates under mild reaction conditions. This review provides an overview on the use of anodic electrochemical methods for expediting the development of carbon–hydrogen functionalization and carbon–nitrogen bond formation strategies. Emphasis is placed on methodology development and mechanistic insight and aims to provide inspiration for future synthetic applications in the field of electrosynthesis.

626 citations

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TL;DR: This review provides a comprehensive survey of the electrochemical properties and electrocatalytic applications of aminoxyls, imidoxylS, and related reagents, of which the two prototypical and widely used examples are 2,2,6,6-tetramethylpiperidine N-oxyl (TEMPO) and phthalimide N- oxyl (PINO).
Abstract: N-Oxyl compounds represent a diverse group of reagents that find widespread use as catalysts for the selective oxidation of organic molecules in both laboratory and industrial applications. While turnover of N-oxyl catalysts in oxidation reactions may be accomplished with a variety of stoichiometric oxidants, N-oxyl reagents have also been extensively used as catalysts under electrochemical conditions in the absence of chemical oxidants. Several classes of N-oxyl compounds undergo facile redox reactions at electrode surfaces, enabling them to mediate a wide range of electrosynthetic reactions. Electrochemical studies also provide insights into the structural properties and mechanisms of chemical and electrochemical catalysis by N-oxyl compounds. This review provides a comprehensive survey of the electrochemical properties and electrocatalytic applications of aminoxyls, imidoxyls, and related reagents, of which the two prototypical and widely used examples are 2,2,6,6-tetramethylpiperidine N-oxyl (TEMPO) a...

537 citations

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TL;DR: In this review, three very different synthetic challenges-the generation and trapping of radical cations, the development of site-selective reactions on microelectrode arrays, and the optimization of current in a paired electrolysis-are used to illustrate this point.
Abstract: While organic electrochemistry can look quite different to a chemist not familiar with the technique, the reactions are at their core organic reactions. As such, they are developed and optimized using the same physical organic chemistry principles employed during the development of any other organic reaction. Certainly, the electron transfer that triggers the reactions can require a consideration of new “wrinkles” to those principles, but those considerations are typically minimal relative to the more traditional approaches needed to manipulate the pathways available to the reactive intermediates formed downstream of that electron transfer. In this review, three very different synthetic challenges—the generation and trapping of radical cations, the development of site-selective reactions on microelectrode arrays, and the optimization of current in a paired electrolysis—are used to illustrate this point.

414 citations