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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: In this paper, a preparative method was developed for the synthesis of dialkylacetic acids by the addition of acids of normal structure to α-olefins and the relation was determined of the yields of 1 ∶: 1 adducts to the reaction temperature and time, the amount of t-butyl peroxide used, and the molar ratio of acid: olefin.
Abstract: 1. A preparative method was developed for the synthesis of dialkylacetic acids by the addition of acids of normal structure to α-olefins. 2. A study was made of the reactivities of acids of different molecular weight and structure and of different a-olefins in this reaction. 3. The relation was determined of the yields of 1 ∶: 1 adducts to the reaction temperature and time, the amount of t-butyl peroxide used, and the molar ratio of acid: olefin.

2 citations

Journal ArticleDOI
TL;DR: In this paper, it was shown that the principal path followed in the oxidative addition of acetone to aromatic compounds (ArH) under the action of Mn(III) acetate in AcOH solution to be the formation of a [CH2=C(CH3)-OMnIII·ArH] complex, which breaks down with rupture of the MnIII-O bond and subsequent addition of the acetonyl radical to the coordinated ArH (limiting step); this is, in turn, followed by rapid one-electron oxidation of the intermediate adduct radical
Abstract: Kinetic data indicate that the principal path followed in the oxidative addition of acetone to aromatic compounds (ArH) under the action of Mn(III) acetate in AcOH solution to be the formation of a [CH2=C(CH3)-OMnIII·ArH] complex, which breaks down with rupture of the MnIII-O bond and subsequent addition of the acetonyl radical to the coordinated ArH (limiting step); this is, in turn, followed by rapid one-electron oxidation of the intermediate adduct radical by the Mn(III) ion, and formation of the final product.

1 citations

Journal ArticleDOI
TL;DR: In this article, the relative content of an individual chloroalkanonitrile in the mixture of isomers increased depending on the extent of removal of the radical center from the CN group in the intermediate cyanoalkyl radicals, reaching a maximum on substitution at the (ω-1)-th carbon atom.
Abstract: 1 Oxidative chlorination of alkanonitriles CH3(CH2)nCN (n=2–6) with sodium persulfate in the presence of an equimolar quantity of copper chloride in water and in hydrochloric acid occurred at each carbon atom of the alkyl chain with the exception of theα position 2 On reaction in water the relative content of an individual chloroalkanonitrile in the mixture of isomers increased depending on the extent of removal of the radical center from the CN group in the intermediate cyanoalkyl radicals, reaching a maximum on substitution at the (ω-1)-th carbon atom 3 On reaction in hydrochloric acid 5-chloroalkanonitriles were formed predominantly which indicated the intramolecular participation of the cyano group in the generation of the intermediate 4-cyanoalkyl radicals

1 citations


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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