Yu. N. Ogibin

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.

Electrochemical Synthesis of Geminal Azidonitro Compounds.

Abstract: An electrochemical method for the synthesis of geminal azidonitro compounds was developed. The method involves electrooxidative coupling of azide anions with salts of nitro compounds and affords geminal azidonitroalkanes, azidonitrocycloalkanes, and diazidodinitrocycloalkanes in 45–92% yields.

Oxidative cyclization of ω-carboxyalkyl radicals

Abstract: 1. The 3-carboxypropyl and 4-carboxybutyl radicals were generated by the respective decarboxylation of glutaric and adipic acids at 60°C in aqueous solution under the influence of Na2S2O8 in the presence of a catalytic amount of AgNO3, and their transformations under the decarboxylation conditions were studied, and also the effect of added copper ions on these transformations. 2. The system Na2S2O8-AgNO3-CuSO4 causes an efficient oxidative cyclization of the studiedω-carboxyalkyl radicals, in which connection the 3-carboxypropyl radicals are selectively converted toγ-butyrolactone, while the 4-carboxybutyl radicals are converted to δ-valerolactone to the extent of 90%. 3. Oxidative cyclization also occurs in the absence of copper ions, but its contribution to the sum of the transformations of the 3-carboxypropyl radicals does not exceed 50%, and not over 30% in the case of the 4-carboxybutyl radicals.

Free-radical addition of aliphatic carboxylic acids to dialkyldiallylsilanes

Abstract: When reaction is initiated with t-butyl peroxide, carboxylic acids add to one double bond of dialkyldially lsilanes with subsequent homolytic intramolecular cyclization of the intermediately formed free radical with formation of a compound containing a silicon atom in a six-membered ring.

Free radical addition of alkanoic esters to alkyl maleates

Abstract: 1. The reaction, initiated by tert-butyl peroxide, of the C1-C5 alkyl esters of alkanoic acids, excluding the ethyl alkanoates, with alkyl maleates gives only the addition products at the acyl group of the ester, in which connection the propionates and isobutyrates react regioselectively at the α-C atom, while the other esters react predominantly at the α- and (ω-1)-C atoms. 2. Hexyl acetate, octyl formate, and ethyl benzoate under analogous conditions add to alkyl maleates at the alkoxyl group (ethyl benzoate reacts regioselectively at the α-C atom, while hexyl acetate and octyl formate react predominantly at the (ω-1)-C atom. 3. γ-Butyrolactone and the alkyl maleate form the addition products at both theα- and γ-c atoms of butyrolactone in an ∿4∶1 ratio.

Redox catalysis in organic electrosynthesis: basic principles and recent developments.

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.

Synthetic Organic Electrochemistry: An Enabling and Innately Sustainable Method

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.

Electrochemical strategies for C-H functionalization and C-N bond formation.

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.

Tetramethylpiperidine N-Oxyl (TEMPO), Phthalimide N-Oxyl (PINO), and Related N-Oxyl Species: Electrochemical Properties and Their Use in Electrocatalytic Reactions.

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...

Using Physical Organic Chemistry To Shape the Course of Electrochemical Reactions.

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.