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Science China chemistry 2024年第9期67卷 2982-2988页

作者： En-He Huang Li-Gao Liu You-Wei Yin Hao-Xuan Dong Ji-Jia Zhou Xin Lu Bo Zhou Long-Wu Ye Key laboratory for Chemical Biology of Fujian Province and State Key laboratory of physical chemistry of Solid Surfaces College of Chemistry and Chemical EngineeringXiamen UniversityXiamen 361005China State Key laboratory of Organometallic chemistry Shanghai Institute of Organic ChemistryChinese Academy of SciencesShanghai 200032China

α-Imino metal carbenes are versatile intermediates in organic synthesis,and have broad applications in the assembly of divergent ***,the catalytic enantioselective desymmetrization based onα-imino metal carbenes has not been developed to ***,we disclose an enantioselective desymmetrizing C(sp^(2))-H functionalization of azide-ynamides viaα-imino copper carbenes,leading to the efficient assembly of divergent chiral indoloazepines in generally moderate to excellent yields with high ***,this reaction represents the first enantioselective desymmetrization based onα-imino metal *** synthetic transformations and biological tests show the potential utility of this ***,computational studies are employed to elucidate the reaction mechanism and the origin of enantioselectivity.

关键词： enantioselective desymmetrization metal carbenes copper catalysis nitrene transfer alkynes

Cucurbit[8]uril-based non-covalent heterodimer realized NIR cell imaging through topological transformation from nanowire to nanorod

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Chinese Chemical Letters 2024年第10期35卷 288-294页

作者： Jianqiu Li Yi Zhang Songen Liu Jie Niu Rong Zhang Yong Chen Yu Liu College of chemistry State Key Laboratory of Elemento-Organic Chemistry Nankai University

In recent years,multicolor cascade supramolecular assemblies with controllable topological morphology have become a research hotspot due to their wide application in light-emitting materials,cell imaging and other ***,several kinds of macrocycles including cucurbiturils,calixarene and cyclodextrins are used as building blocks to construct fluorescent assemblies with anthryl-conjugated phenylpyridine（G）,wherein cucurbit[8]uril （CB[8]） and G can form nanowires at a stoichiometric ratio of n:n through host-guest encapsulation to form a non-covalent ***,the macrocycle confinement effect drastically enhances the fluorescence emission of G and emission peak generated bathochromic shift from 500 nm to 600 *** the supramolecular polymer is further assembled with amphiphilic calix[4]arene （SC4A8）,the fluorescence emission of G?CB[8]further increases to 1.4 times,accompanied by the morphological transformation from linear structure to nanorod ***,a very small amount of dye Cy5 is added to the assembly solution as an energy receptor,and the negatively charged G?CB[8]@SC4A8 system is regarded as an energy *** efficient energy transfer process enables near-infrared （NIR） emission at 675 nm with 71%energy transfer efficiency (ΦET) at a donor/receptor ratio of 100:***,the cascade supramolecular assembly has been successfully applied to targeted imaging in the nucleus of HeLa and A549 cancer cells.

关键词： Cucurbituril Morphological transformation Multivalent assemblies Targeted imaging

Spin effect on redox acceleration and regioselectivity in Fe-catalyzed alkyne hydrosilylation

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National Science Review 2024年第2期11卷 155-167页

作者： Peng He Meng-Yang Hu Jin-Hong Li Tian-Zhang Qiao Yi-Lin Lu Shou-Fei Zhu Frontiers Science Center for New organic Matter State Key Laboratory and Institute of Elemento-Organic Chemistry Nankai University

Iron catalysts are ideal transition metal catalysts because of the Earths abundant, cheap, biocompatible features of iron salts. Iron catalysts often have unique open-shell structures that easily undergo spin crossover in chemical transformations, a feature rarely found in noble metal catalysts. Unfortunately, little is known currently about how the open-shell structure and spin crossover affect the reactivity and selectivity of iron catalysts, which makes the development of iron catalysts a low efficient trial-and-error program. In this paper, a combination of experiments and theoretical calculations revealed that the iron-catalyzed hydrosilylation of alkynes is typical spin-crossover catalysis. Deep insight into the electronic structures of a set of well-defined open-shell active formal Fe(0) catalysts revealed that the spin-delocalization between the iron center and the 1,10-phenanthroline ligand effectively regulates the iron center's spin and oxidation state to meet the opposite electrostatic requirements of oxidative addition and reductive elimination, respectively,and the spin crossover is essential for this electron transfer process. The triplet transition state was essential for achieving high regioselectivity through tuning the nonbonding interactions. These findings provide an important reference for understanding the effect of catalyst spin state on reaction. It is inspiring for the development of iron catalysts and other Earth-abundant metal catalysts, especially from the point of view of ligand development.

关键词： spin effect spin-delocalization spin crossover iron-catalysis alkyne hydrosilylation

Ligand-controlled NiH-catalyzed regiodivergent hydroalkylation of 2-alkenylazaarenes

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Science China chemistry 2024年第6期67卷 1935-1940页

作者： Ya-Ping Shao Zhuo-Min Chi Yong-Min Liang State Key laboratory of Applied organic chemistry School of Chemistry and Chemical EngineeringLanzhou UniversityLanzhou730000China

A nickel-hydride(Ni H)-catalyzed migratory and nonmigratory hydroalkylation reaction of 2-alkenyl azaarenes with alkyl iodines has been established through strategic modulation of N-or P-donor *** method enables the synthesis of diverseβ-orγ-branched aromatic *** mild regiodivergent protocols exhibit wide substrate scope,excellent functional tolerance,and great reaction yield with remarkable ***,deuterium labeling studies reveal Ni H-catalyzed interrupted chain-walking mode as the mechanism behind remotedβ-selective hydroalkylation reaction—an interesting phenomenon mediated through aromatic imine directing groups.

关键词： NiH regiodivergent hydroalkylation azaarenes interrupted chain-walking

Copper-catalyzed asymmetric dearomatizing amination of 2-naphthols:Csp^(2)–N coupling via 1,3-reductive elimination

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Science China chemistry 2024年第8期67卷 2694-2700页

作者： Aying Yihuo Maoping Pu Zheng Tan Jibang Liao Jiuqi Tan Qi-Lin Zhou Xiaohua Liu Xiaoming Feng Key laboratory of Green chemistry&Technology Ministry of EducationCollege of ChemistrySichuan UniversityChengdu 610064China Key laboratory and Institute of Elemento-organic chemistry College of Chemistry Frontiers Science Centerfor New Organic MatterNankai UniversityTianjin300071China

An efficient catalytic asymmetric dearomatizing amination of 2-naphthols and phenols catalyzed by N,N′-dioxide-copper(I)complex as a chiral catalyst was presented.A variety of optically activeβ-naphthalenone compounds with a nitrogen-containing quaternary carbon stereocenter were obtained with high yield and enantioselectivity under mild reaction *** studies indicated that this Csp^(2)–N dearomatizing coupling proceeds via 1,3-reductive elimination of phenolate-Cu~Ⅲ-amino intermediate in five-membered ring transition *** origin of enantioselectivity has also been elucidated based on density functional theory calculations.

关键词： asymmetric catalysis amination dearomatization copper catalysis coupling reaction

The chlorine evolution reaction promoted by organocatalysts with amide functional groups

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Science China chemistry 2024年第3期67卷 749-750页

作者： Lan Zhao Liang-Nian He State Key laboratory and Institute of Elemento-organic chemistry College of ChemistryNankai UniversityTianjin 300071China

Since the nineteenth century, the chlor-alkali process entails the electrochemical oxidation of sodium chloride solutions to Cl_(2) by the chlorine evolution reaction(CER) and the simultaneous production of sodium hyd... 详细信息

关键词： chlorine hydroxide promoted

Illuminating spin-crossover octanuclear metal-organic cages

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Science China chemistry 2024年第4期67卷 1208-1215页

作者： Zhi-Kun Liu Alyona A.Starikova Yu-Xia Li Ke Sun Meng Yu Zi-Shuo Yao Jun Tao Key laboratory of Cluster Science of Ministry of Education School of Chemistry and Chemical EngineeringLiangxiang CampusBeijing Institute of TechnologyBeijing 102488China Institute of physical and organic chemistry Southern Federal UniversityRostov-on-Don 344090Russia

Spin-crossover(SCO)materials that reversibly switch between high-and low-spin states have potential for the storage of spin state-relative information,and have gained much attention incorporating secondary physical properties,such as fluorescence and magneto-optical *** this study,we synthesized three octanuclear metal-organic cages(MOCs)using tetraphenylethylene-based luminophores,aldehydes,and Fe^(Ⅱ)salts,by subcomponent self-assembly approach,namely[Fe1]-[Fe3].By controlling the ligand-field strength and guest encapsulation,we finely tuned their SCO *** them,MOC[Fe2]displayed nearly complete SCO behavior in the solid state,which is rare for high-nuclearity *** also demonstrated the coupling of SCO with fluorescence emission in these MOCs by using isostructural Zn^(Ⅱ)complexes([Zn1]-[Zn3])as control experiments,for the first *** calculations revealed the energy-transfer mechanism between fluorophores and SCOactive centers,which emphasizes the significant contribution of d-d transitions in the interplay between the occurrence of SCO and fluorescence emission.

关键词： metal-organic cages spin crossover fluorescence switching materials DFT calculation

In situ crosslink polymerization induced long-lived multicolor supramolecular hydrogel based on modifiedβ-cyclodextrin

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Chinese Chemical Letters 2024年第2期35卷 374-379页

作者： Yonghui Sun Linnan Jiang Yong Chen Yu Liu College of chemistry State Key Laboratory of Elemento-Organic Chemistry Nankai UniversityTianjin 300071China

The construction of hydrogels with good mechanical properties and phosphorescent properties is full of ***,we report a supramolecular phosphorescent hydrogel with long lifetime,high tensile strength and self-healing property,which can be easily constructed through in-situ thermalinitiated polymerization of isocyanatoethyl acrylate-modifiedβ-cyclodextrin(β-CD-DA)and acrylatemodified adamantane(Ad-DA),acrylic acid(AA),followed by the non-covalent association with carbon dots(CNDs).The lifetime of phosphorescent hydrogel can reach 1261 ms at room temperature,and the quantum yield is 11%.Importantly,through the efficient triplet to singlet Förster resonance energy transfer(TS-FRET),the phosphorescent hydrogel shows the good phosphorescence energy transfer property for organic dyes Rhodamine B and Eosin Y with the delayed fluorescence lifetime up to 730 ms and 585 ms as well as the energy transfer efficiency(Φ_(ET))up to 99.9%and 99.3%,***,owing to the host-guest interactions betweenβ-CD-DA and Ad-DA,the three-dimensional cross-linked network phosphorescent hydrogel can be easily stretched to 18 times of its original length,and can achieve self-healing of the cut surfaces within 30 *** results will expand the scope of phosphorescent materials and provide new ideas and opportunities for materials science.

关键词： Room temperature phosphorescence Hydrogel Phosphorescence energy transfer Cyclodextrin Supramolecular interaction

Performance enhancement and active sites identification of Cu-Cd bimetallic oxide derived catalysts for electrochemical CO_(2) reduction

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Journal of Energy chemistry 2024年第4期91卷 50-58页

作者： Cai Wang Xin Hu Bairong Chen Houan Ren Xiaoyu Wang Yilin Zhang Xinyu Chen Yuping Liu Qingxin Guan Wei Li State Key laboratory of Elemento-organic chemistry Key Laboratory of Adv.Energy Mater.Chemistry(Ministry of Education)College of ChemistryNankai UniversityTianjin 300071China

The development of earth-abundant electrocatalysts with high performance for electrochemical CO_(2)reduction(ECR)is of great ***-based catalysts have been widely investigated for ECR due to their unique ability to generate various carbonaceous products,but directing selectivity toward one certain product and identifying the real active sites during ECR are still full of ***,after the incorporation of CdO into CuO,the Cu_(0.5)Cd_(0.5)-O catalyst achieves a 10.3-fold enhancement for CO selectivity in comparison with CuO,and a CO faradic efficiency nearly 90%with a current density around20 mA cm^(-2)could maintain at least 60 ***,a wide CO/H_(2)ratio(0.07-10)is reached on Cu_(x)Cd_(1-x)-O catalysts by varying the Cu/Cd ratio,demonstrating the potential of syngas production using such *** results of ex situ XRD,XPS,and in situ Raman reveal that the real active sites of Cu_(0.5)Cd_(0.5)-O catalysts for CO production during ECR reaction are the reconstructed mixed phases of CuCd alloy and CdCO_(3).In situ FTIR and theoretical calculations further implicate the presence of Cd related species promotes the CO desorption and inhibits the H_(2)evolution,thus leading to an enhanced CO generation.

关键词： CO_(2)reduction Cu-Cd bimetallic Real active sites CO production

Cobalt(Ⅲ)hydride HAT mediated enantioselective intramolecular hydroamination access to chiral pyrrolidines

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Science China chemistry 2024年第6期67卷 2002-2008页

作者： Qi Meng Tao Qin Huanran Miao Ge Zhang Qian Zhang Jilin Province Key laboratory of organic Functional Molecular Design&Synthesis Department of ChemistryNortheast Normal UniversityChangchun130024China State Key laboratory of Organometallic chemistry Shanghai Institute of Organic ChemistryChinese Academy of SciencesShanghai200032China

Enantioenriched pyrrolidines and derivatives are ubiquitous substructures in compounds of importance to medicinal and biological ***,we report an efficient cobalt-catalyzed intramolecular asymmetric hydroamination reaction that produces chiral pyrrolidines with good to excellent yield and *** with previously reported radicalinvolved methodologies for enantioenriched pyrrolidines,these conditions feature two elegant versatilities,enabling(1)the use of cobalt-catalyzed hydrogen atom transfer(HAT)to generate organocobalt intermediates that bring radical reaction to organometallic chemistry,and(2)enantioselective intramolecular C-N bond forging through an S_(N)2-like displacement involving dynamic kinetic resolution(DKR).This approach provides a new alternative and efficient methodology for enantioselective radical-involved C-N bond construction that can be used in the synthesis of both chiral pyrrolidines and homologous nitrogen heterocycles.

关键词： asymmetric catalysis radical hydroamination cobalt catalysis hydrogen atom transfer