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G. I. Nikishin

Bio: G. I. Nikishin is an academic researcher from Russian Academy of Sciences. The author has contributed to research in topics: Radical & Homolysis. The author has an hindex of 11, co-authored 280 publications receiving 540 citations.


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TL;DR: The main product of the reaction of 1-methylcyclobutanol with Pb(OAc)4 in benzene is 1-phenyl-4-pentanone as discussed by the authors.
Abstract: The main product of the reaction of 1-methylcyclobutanol with Pb(OAc)4 in benzene is 1-phenyl-4-pentanone; the use of Mn(OAc)3 in acetic acid gives a mixture of 2,9-decanedione and methyl propyl ketone; 1-(chloro-, bromo-, thiocyano-, or cyano)-4-pentanone is formed in the presence of the systems Pb(OAc)4-metal halide or Mn(OAc)3-metal halide.
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TL;DR: In this paper, the thermal decomposition of peroxydisuccinic acid and its dimethyl ester was studied in acetic acid, benzene, and isopropanol.
Abstract: 1. The thermal decomposition of peroxydisuccinic acid and its dimethyl ester was studied in acetic acid, benzene, and isopropanol. In benzene and acetic acid, a first order of the reaction with respect to the peroxide is observed. 2. Products of thermal decomposition of the peroxides were identified and a mechanism of their formation was proposed. 3. Radicals formed from peroxydisuccinic acid under the action of UV irradiation and as a result of secondary reactions in the absence of irradiation were investigated by the EPR method. A mechanism of photodecomposition with the participation of radical pair was proposed.
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TL;DR: In this paper, the 3-carboxypropyl 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 also the effect of added copper ions on these transformations.
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.
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TL;DR: The rate constant for the breakdown of peroxydiglutaric acid (I) in benzene and toluene remains essentially unaltered as the pressure is raised to 10, 000 kg/cm2 as discussed by the authors.
Abstract: 1. The rate constant for the breakdown of the dimethyl ester of peroxydiglutaric acid (I) in benzene and toluene remains essentially unaltered as the pressure is raised to 10, 000 kg/cm2. 2. Breakdown of (I) can proceed with rupture of the O-O bond (ka) or with the rupture of three bonds and the evolution of two molecules of CO2 (kb). 3. Increasing the pressure increases proportion of radical reaction products formed through rupture of the O-O bond. 4. The rate constant kb, diminishes with rising pressure. 5. Increasing the pressure decreases the probability of radical reaction in the cage as compared with the probability of radical passage out of the cage.

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08 Dec 2001-BMJ
TL;DR: There is, I think, something ethereal about i —the square root of minus one, which seems an odd beast at that time—an intruder hovering on the edge of reality.
Abstract: There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality. Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

33,785 citations

Journal ArticleDOI
TL;DR: Recent progress in the field of organometallic cobalt-catalyzed C–H activation is reviewed until November 2015.
Abstract: Catalytic C–H activation has emerged as a powerful tool for sustainable syntheses. In the recent years, notable success was achieved with the development of cobalt-catalyzed C–H functionalizations with either in situ generated or single-component cobalt-complexes under mild reaction conditions. Herein, recent progress in the field of organometallic cobalt-catalyzed C–H activation is reviewed until November 2015.

953 citations

Journal ArticleDOI
TL;DR: This analysis comprehensively review all asymmetric transition-metal-catalyzed methodologies that are believed to proceed via an inner-sphere-type mechanism, with an emphasis on the nature of stereochemistry generation.
Abstract: The development of new methods for the direct functionalization of unactivated C–H bonds is ushering in a paradigm shift in the field of retrosynthetic analysis. In particular, the catalytic enantioselective functionalization of C–H bonds represents a highly atom- and step-economic approach toward the generation of structural complexity. However, as a result of their ubiquity and low reactivity, controlling both the chemo- and stereoselectivity of such processes constitutes a significant challenge. Herein we comprehensively review all asymmetric transition-metal-catalyzed methodologies that are believed to proceed via an inner-sphere-type mechanism, with an emphasis on the nature of stereochemistry generation. Our analysis serves to document the considerable and rapid progress within in the field, while also highlighting limitations of current methods.

648 citations