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Adding new dimension to non-directed C（sp3）–H functionalizations

Science China Chemistry 2025年

作者： konstantin p.bryliakov Laboratory of Selective Oxidation Catalysis N.D.Zelinsky Institute of Organic Chemistry RAS

Aliphatic C–H groups are among the most abundant yet least reactive functional groups in organic molecules. Nature has evolved metalloenzymes such as those of the cytochrome p450 superfamily that efficiently activate individual tertiary（3） and secondary （2） C（sp3）–H bonds in complex molecules with the highest level of regio-and stereoselectivity [1], thus encouraging studies aimed at engineering artificial metalloenzymes for synthetic applications [2].

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Chemical Mechanisms of prebiotic Chirality Amplification

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Research 2020年第1期2020卷 914-921页

作者： konstantin p.bryliakov Novosibirsk State University Pirogova 1Novosibirsk 630090Russia Boreskov Institute of Catalysis Pr.Lavrentieva 5Novosibirsk 630090Russia

This review article surveys the recent experimental findings that suggest alternative chemical models of directed chirality amplification at the early,prebiotic *** is believed that the chirality amplification step followed the initial emergence of small enantiomeric imbalance and preceded(as a necessary condition)the occurrence of homochiral biopolymers,assembled from enantiomerically pure building *** work focuses on the chemical nature of possible mechanisms of primordial chirality enhancement,without going into detail of the preceding and subsequent phases of origination of biological homochirality and life on *** mechanisms are discussed through the prism of integrity of biological natural selection and chemical kinetic selection.

关键词： Chiral subsequent finding

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New family of single-component Ni catalysts for ethylene polymerization to high and ultrahigh molecular weight polyethylene

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Science China Chemistry 2020年第6期63卷 753-754页

作者： Artem A.Antonov Wen-Hua Sun konstantin p.bryliakov Boreskov Institute of Catalysis Pr.Lavrentieva 5Novosibirsk 630090Russia Novosibirsk State University Pirogova 1Novosibirsk 630090Russia Key Laboratory of Engineering plastics and Beijing National Laboratory for Molecular Sciences Institute of ChemistryChinese Academy of SciencesBeijing 100190China CAS Research/Education Center for Excellence in Molecular Sciences University of Chinese Academy of SciencesBeijing 100049China

Since the milestone discovery of Ni(II)salicylaldiminate catalysts by Grubbs and co-workers[1],nickel(II)complexes with N,N-and N,O-donor ligands have strengthened their lead in the search for highly active platforms for olefins homo-and copolymerization with various co-monomers,including those with polar groups,to achieve polymers with precisely controlled microstructures[2,3].

关键词： discovery catalysts co-monomers

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Ni catalyzed ethylene copolymerization with polar monomers

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Science China Chemistry 2019年第6期62卷 653-654页

作者： Igor E.Soshnikov Changle Chen konstantin p.bryliakov Boreskov Institute of Catalysis Novosibirsk State University Hefei National Laboratory for physical Sciences at the Microscale CAS Key Laboratory of Soft Matter Chemistry Department of Polymer Science and Engineering University of Science and Technology of China

Introduction of polar comonomers into polyethylene is highly challenging,paving the way to tuning the copolymers'mechanical properties,adhesion/compatibility,and ***-group tolerant single-site palladium and,more tempting,nickel-based catalysts have demon-strated promising reactivities in the ethylene copolymerization with polar comonomers via coordination/insertion mechanism。

关键词： Introduction polyethylene mechanism

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Chiral Autoamplification Meets Dynamic Chirality Control to Suggest Nonautocatalytic Chemical Model of prebiotic Chirality Amplification

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Research 2019年第1期2019卷 318-326页

作者： Evgenii p.Talsi Anna A.bryliakova Roman V.Ottenbacher Tatyana V.Rybalova konstantin p.bryliakov Novosibirsk State University Pirogova 2Novosibirsk 630090Russia Boreskov Institute of Catalysis Pr.Lavrentieva 5Novosibirsk 630090Russia Vorozhtsov Novosibirsk Institute of Organic Chemistry Pr.Lavrentieva 9Novosibirsk 630090Russia

Oxidative kinetic resolution of 1-phenylethanol in the presence of manganese complexes,bearing conformationally nonrigid achiral bis-amine-bis-pyridine ligands,in the absence of any exogenous chiral additives,is *** only driving force for the chiral discrimination is the small initial enantiomeric imbalance of the scalemic(nonracemic)substrate:the latter dynamically controls the chirality of the catalyst,serving itself as the chiral *** effect,the ee of 1-phenylethanol increases monotonously over the reaction *** dynamic control of catalyst chirality by the substrate has been unprecedented;a consistent kinetic model for this process is *** reported catalyzed substrate self-enantioenrichment mechanism is discussed in relation to the problem of prebiotic chirality amplification.

关键词： chiral Chiral catalyst

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