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Science China chemistry 2025年第1期68卷 257-263页

作者： Jiapian Huang Chenxin Wang Xu Wang Xiaoyu Zhou Wei Xiao Jie Wu School of Pharmaceutical and Chemical Engineering & institute for Advanced Studies Taizhou University State Key Laboratory of Organometallic chemistry Shanghai Institute of Organic Chemistry Chinese Academy of Sciences School of chemistry and Chemical Engineering Henan Normal University

The generation of various β-chiral sulfones bearing chiral cyclic sulfinamides through photoredox-catalyzed sulfur dioxide insertion with asymmetric radical cyclization is described. This method features a broad substrate scope and excellent stereospecificity. Computational studies reveal that the dispersion interaction between sulfinyl group and CH2SO2Ph group plays a crucial role in the stereoselectivity control.

关键词： β-chiral sulfones chiral cyclic sulfinamides sulfur dioxide insertion asymmetric radical cyclization stereoselectivity

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

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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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Synthesis of chiral phosphine derivatives through a copper（I）-catalyzed desymmetric SNAr reaction

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Science China chemistry 2025年

作者： Shuai Zhang Pei-Zhi Liu Yan-Bo Li Qi Zhang Jun-Zhao Xiao Yi-Fan Wang Tian-Yu Wei Jia-Wei Jiang Ye Wang Qian Peng Liang Yin Key Laboratory of Fluorine and Nitrogen chemistry and Advanced Materials Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences State Key Laboratory of Elemento-organic chemistry and Tianjin Key Laboratory of Biosensing and Molecular Recognition College of Chemistry Frontiers Science Center for New Organic Matter Nankai University Haihe Laboratory of Sustainable Chemical Transformations

Axially chiral phosphines are a class of extremely important ligands in asymmetric catalysis. Herein, an unprecedented copper（I）-catalyzed asymmetric SNAr reaction with HP（S）R2is uncovered, which delivers a series of axially chiral phosphine derivatives in high yields with excellent enantioselectivity. Furthermore, the diastereoselective reaction with the kinetic resolution of racemic HP（S）ArR proceeds smoothly, providing the products with moderate diastereoselectivity and excellent enantioselectivity. Control experiments indicate that HP（S）Ph2is much more active than HPPh2and HP（O）Ph2as the pronucleophile in the present reaction. It is found that the SNAr reaction （the first SNAr） proceeds in a desymmetric manner, providing the desired chiral products while a continued SNAr reaction （the second SNAr） slightly occurs in a kinetic resolution manner in the present catalytic system, which enhances the ee of the desired chiral products. DFTcalculations support a concerted reaction pathway rather than a step-wise mechanism. Finally, axially chiral olefin-phosphines produced by the present method work as suitable ligands in Pdcatalyzed asymmetric allylic substitution with C-, N-, and O-nucleophiles and Rh-catalyzed asymmetric addition of arylboronic acid to benzil.

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Recent progress on photoactive nonprecious transition-metal complexes

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Science China chemistry 2025年第1期68卷 46-95页

作者： Zhong-Liang Gong Hong-Jie Zhang Yan Cheng Jianxun Liu Yuhan Ai Yaqin Li Zhihui Feng Qiong Zhang Shaolong Gong Yong Chen Chang-Jiang Yao Yuan-Yuan Zhu Liang-Jin Xu Yu-Wu Zhong CAS Key Laboratory of Photochemistry Institute of Chemistry Chinese Academy of Sciences State Key Laboratory of Structural Cemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences School of chemistry and Chemical Engineering Anhui Key Laboratory of Advanced Catalytic Materials and Reaction EngineeringHefei University of Technology State Key Laboratory of Explosion Science and Safety Protection School of Mechatronical Engineering Beijing Institute of Technology College of chemistry and Molecular Sciences Hubei Key Lab on Organic and Polymeric Optoelectronic Materials Wuhan University School of chemistry and Chemical Engineering Anhui University Key Laboratory of Photochemical Conversion and Optoelectronic Materials & CAS-HKU Joint Laboratory on New Materials Technical Institute of Physics and Chemistry Chinese Academy of Sciences

Photoactive complexes of nonprecious transition metals, mainly including those in the first-row and partially the second-row of the Periodic table of elements, have received increasing attention in view of their low cost and long-term sustainability. They are recognized as promising alternatives to noble transition metal complex congeners that have been extensively studied in optoelectronic devices, artificial photosynthesis, photocatalysis, biodiagnostics, and therapeutics, etc. This review is devoted to a comprehensive summary on the classical and recent advances on photoactive nonprecious transition metal complexes, including photoactive Zr, V, Cr, Mo, and W complexes, Mn complexes and hybrids, Fe, Co, Ni, and Cu complexes, and Zn and Cd complexes and hybrids. A particular focus is given on the molecular design, modulation of photophysical and photochemical properties, and applications of the representative and lately-developed nonprecious metal complexes. In addition, a perspective on the future development in this field is provided at the end of this review.

关键词： photoactive metal complexes earth-abundant metals nonprecious metal complexes luminescence photochemistry

Bifunctional bridging capping layer enables 24.5% efficiency of perovskite solar cells with polymer-based hole transport materials

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Science China chemistry 2025年第1期68卷 350-359页

作者： Can Zhu Yiyang Wang Lei Meng Beibei Qiu Jing Li Shucheng Qin Ke Hu Xin Jiang Wenbin Lai Minchao Liu Zhe Liu Chenxing Lu Jinyuan Zhang Yongfang Li Beijing National Laboratory for Molecular Sciences CAS Key Laboratory of Organic Solids Institute of Chemistry Chinese Academy of Sciences School of Chemical Science University of Chinese Academy of Sciences Key Laboratory of Solid State Optoelectronic Devices of Zhejiang Province College of Physics and Electronic Information Engineering Zhejiang Normal University Key Laboratory of Photochemical Conversion and Optoelectronic Materials Technical Institute of Physics and ChemistryChinese Academy of Sciences Laboratory of Advanced Optoelectronic Materials College of Chemistry Chemical Engineering and Materials ScienceSoochow University

Developing a bridge capping layer between perovskite and hole transport layer materials（HTMs） in the n-i-p perovskite solar cells（pero-SCs） is an effective approach to modify the morphology of HTMs and passivate the perovskite ***, we select the quinoxaline-based bifunctional passivation agent, quinoxalin-6-yl-methylamine hydrochloride（Qx MACl）,as the bridging layer, and a D-A copolymer PBQ12 containing the same quinoxaline unit as an HTM for the n-i-p pero-SCs. Due to the π-π stacking among the common quinoxaline units in the bridge layer and HTM, Qx MACl induces the π-π stacking of the PBQ12 film and improves the film morphology of HTMs with better conductivity. Additionally, Qx MACl can effectively passivate the perovskite surface, and PBQ12 possesses appropriate energy levels and high hole mobility. The pero-SCs based on FAPbI3with PBQ12/Qx MACl treatment showed a higher power conversion efficiency（PCE） of 24.05% and outstanding stability, maintaining 95.4% and 92.1% of its initial PCE after 750 h of storage and after over 800 h of thermal annealing at 85 °C, respectively. To further enhance the PCE of the PBQ12/Qx MACl-based devices, we developed a non-metal ion dopant for the PBQ12 HTM. Through trace doping of PBQ12 HTM by the non-metal ion dopant, the PCE of the PBQ12/Qx MACl-based devices reached 25.24%（the calibrated PCE of 24.55% by the National institute of Metrology, China）.

关键词： D-A copolymer, hole transport materials, bifunctional bridge capping layer, passivation perovskite solar cells

Photosynthetic reaction pathways of natural and artificial systems

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Science China chemistry 2025年

作者： Shixing Lei Liting Bi Lingxuan Chen Zhanting Li Jia Tian State Key Laboratory of Organometallic chemistry and Shanghai Hong Kong Joint Laboratory in Chemical Synthesis Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences

Photosynthesis converts solar energy into chemical energy through highly coordinated photosynthetic *** by natural systems,artificial photosynthesis aims to develop an efficient,sustainable,and cost-effective pathway for solar-tochemical *** review examines natural photosynthetic pathways,including retinal/rhodopsin-,bacteriochlorophyll-,and chlorophyll-based systems,highlighting their key components and ***,we outline reaction pathways in artificial photosynthetic systems constructed via heterogeneous,homogeneous,self-assembly,and semi-artificial strategies,focusing on water splitting,carbon fixation,and nitrogen ***,we offer insights into future directions for artificial photosynthesis,emphasizing the importance of using self-assembly strategies and the potential of using primitive phototrophic microorganisms as models.

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Cyano migration-mediated radical-polar crossover cyclopropanation

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Science China chemistry 2025年第1期68卷 241-248页

作者： Ziqiang Wang Yasu Chen Jie Li Chen Zhu Key Laboratory of organic Synthesis of Jiangsu Province College of Chemistry Chemical Engineering and Materials ScienceSoochow University Frontiers Science Center for Transformative Molecules Zhangjiang Institute for Advanced Study and Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs Shanghai Jiao Tong University

We report a novel cyano migration-mediated radical-polar crossover process, whereby both the sulfonylcyanation of aliphatic alkenes and the formation of cyclopropanes are concurrently achieved. This transformation yields a diverse array of multisubstituted cyclopropanes under mild photocatalytic conditions. Mechanistic studies elucidate that the reaction proceeds via intramolecular nucleophilic substitution, leading to the formation of the cyclopropane derivatives.

关键词： cyclopropanation cyano migration radical-polar crossover radical reactions

Cobalamin-dependent radical S-adenosyl-L-methionine protein functions with a partner to successively methylate tricyclic indole alkaloid for chuangxinmycin maturation and derivatization

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Science China chemistry 2025年第1期68卷 308-316页

作者： Sili Wang Jiancheng Huang Yanan Du Wei Huang Yufeng Xue Xiaokun Xu Guannan Zhong Yuanyuan Shi Bin Hong Xiaoying Bian Wen Liu State Key Laboratory of Chemical Biology Shanghai Institute of Organic Chemistry University of Chinese Academy of SciencesChinese Academy of Sciences State Key Laboratory of Microbial Technology Shandong University National Health Commission (NHC) Key Laboratory of Biotechnology for Microbial Drugs Institute of Medicinal BiotechnologyChinese Academy of Medical Science & Peking Union Medical College

Cobalamin(Cbl)-dependent radical S-adenosyl-L-methionine(SAM) proteins constitute the largest collection of the radical SAM superfamily that has hundreds of thousands of individual members. Many of these proteins are involved in the biosynthesis of pharmaceutically important natural products to catalyze chemically demanding reactions. In the biosynthetic pathway of chuangxinmycin(CXM), a unique indole alkaloid antibiotic with potent anti-infective activity, functionalization of the characteristic thiopyrano[4,3,2-cd]indole scaffold by regio-and stereoselective C3-methylation is believed to rely on a Cbl-dependent radical process, which, however, remained to be reconstituted biochemically. We here report the dissection of this enzymatic process, which requires the incorporation of Cxm8, a Cbl-dependent radical SAM protein, with Cxm9, a DUF5825family protein that shares no homology to any proteins of known functions. Cxm8 and Cxm9 function together by forming an unexpected heterodimeric complex that selectively catalyzes C3-methylation of the tricyclic indole-S-hetero ring system in a successive manner, achieving CXM and a recently identified, C3-dimethylated congener. Detailed biochemical characterization,isotope labeling, structural simulation and bioinformatics analysis rationalized the catalysis of the Cxm8/Cxm9 complex and particularly the necessity of the DUF5825 protein for C3-methylase activity. This is the first example that a Cbl-dependent protein acts with a partner to exhibit radical SAM activity.

关键词： cbl-dependent radical SAM protein biosynthesis chuangxinmycin stereoselective methylation

Enantioselective β-alkenylation of α,β-unsaturated aldehydes via chiral biphosphine ligand modified dirhodium(II) catalysis

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Science China chemistry 2025年

作者： Guangli Xu Hongda Chen Xiaoming Wang State Key Laboratory of Organometallic chemistry and Shanghai Hongkong Joint Laboratory in Chemical Synthesis Center for Excellence in Molecular Synthesis Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences School of chemistry and Materials Science Hangzhou Institute for Advanced Study University of Chinese Academy of Sciences School of chemistry and Chemical Engineering Henan Normal University

Dirhodium(II) complexes have achieved great success in organic synthesis,and fine-tuning their catalytic properties with various bridging ligands is well-investigated in carbene ***,combining dirhodium(II) with a sophisticated ligand as a catalyst in other reactions is still extremely challenging,especially for the asymmetric synthesis of valuable chiral ***,we report a dirhodium(II)/(S)-MeO-BIPHEP catalytic system for the challenging asymmetric β-alkenylation of α,β-unsaturated aldehydes,affording the corresponding chiral conjugate addition products in good yields with high enantioselectivities.A couple of drug-derived substrates were also compatible with the protocol,which has been successfully used to prepare biologically relevant pyranochromene *** mechanistic studies suggested that the dirhodium core might remain intact over the catalytic cycle,and the chiral diphosphine ligand plays a key role in this novel reactivity and determining the high enantioselectivities of the asymmetric conjugate addition.

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Boosting hydrocarbon conversion via Cu-doping induced oxygen vacancies on CeO2 in CO2 electroreduction

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Journal of Energy chemistry 2025年第1期100卷 66-76页

作者： Lei Xue Tong Shi Chenhui Han Heng Zhang Fenrong Liu Haorun Li Yan Wang Xiaojun Gu Shanghong Zeng Inner Mongolia Key Laboratory of chemistry and Physics of Rare Earth Materials School of Chemistry and Chemical Engineering Inner Mongolia University State Key Laboratory of Coal Conversion Institute of Coal Chemistry Chinese Academy of Sciences institute of Catalysis Department of Chemistry Zhejiang University National Key Laboratory of Baiyunobo Rare Earth Resource Research and Comprehensive Utilization Baotou Research Institute of Rare Earths

Conversion of CO2back to hydrocarbons is the most direct way of closing the“carbon cycle”,and its significance is further enlarged if this process is driven by renewable energies such as ***,precisely controlling the product selectivity towards hydrocarbons against the competitive hydrogen evolution remains challenging,especially for Cu-based ***,we report a novel defect engineering strategy,by which Cu-doping-induced oxygen vacancies on CeO2nanorods were effectively created,with adjustable vacancy/Cu *** resulting optimum catalyst shows up to 79% catalytic current density to hydrocarbons （excluding CO）,with 49% faradaic efficiency to *** and density functional theory unveil that the ratio between oxygen vacancy and Cu affects significantly the formation of*CHO and activation of H2O,which leads to the following deep hydrogenation to *** findings may spur new insights for designing and developing more controllable chemical process relevant to CO2utilization.

关键词： Nanorods