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学者姓名:曾程初
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Abstract :
We report an electrochemical radical-polar crossover (RPC) strategy for the radical cyclization of olefinic amides with C-H nucleophiles with H2 as the byproduct. Enabled by this strategy, structurally diverse multi-ester functionalized benzoxazines and iminoisobenzofurans were obtained with good yields. Notably, the resulting triple-ester functionalized O-heterocycles are inaccessible by other means. This protocol features catalyst- and external oxidant-free conditions, high atom economy, and broad substrate scope. The scalable synthesis as well as product derivatization highlight the synthetic utility of this electrochemical protocol.
Keyword :
radical-polar crossover radical-polar crossover radical cascade radical cascade organic electrosynthesis organic electrosynthesis olefinic amide olefinic amide
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GB/T 7714 | Li, Qibin , Bu, Linghua , Xu, Kun et al. Electrochemical Radical-Polar Crossover Enabled Multi-ester Functionalized O-Containing Heterocycles Synthesis [J]. | ADVANCED SYNTHESIS & CATALYSIS , 2025 . |
MLA | Li, Qibin et al. "Electrochemical Radical-Polar Crossover Enabled Multi-ester Functionalized O-Containing Heterocycles Synthesis" . | ADVANCED SYNTHESIS & CATALYSIS (2025) . |
APA | Li, Qibin , Bu, Linghua , Xu, Kun , Zeng, Chengchu . Electrochemical Radical-Polar Crossover Enabled Multi-ester Functionalized O-Containing Heterocycles Synthesis . | ADVANCED SYNTHESIS & CATALYSIS , 2025 . |
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Abstract :
The electrochemical catalyst-free generation of carbon radicals bearing three electron-withdrawing groups from the corresponding C-H nucleophiles remains unexplored. To this end, we report a direct electro-oxidation strategy to access these electrophilic carbon radicals under catalyst-free conditions. Enabled by this strategy, the radical 1,2-alkylarylations of allylic alcohols was realized, affording beta-quaternary ketones with high functional group compatibility. This protocol is operationally simple and also easy to scale up.
Keyword :
Electrochemical umpolung Electrochemical umpolung Organic electrosynthesis Organic electrosynthesis Radical rearrangement Radical rearrangement Electrophilic radical Electrophilic radical
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GB/T 7714 | Li, Qibin , Hu, Die , Xu, Kun et al. Electrochemical Umpolung of C-H Nucleophiles Bearing Three Electron-Withdrawing Groups to Trigger Radical 1,2-Alkylarylations of Allylic Alcohols [J]. | ADVANCED SYNTHESIS & CATALYSIS , 2025 . |
MLA | Li, Qibin et al. "Electrochemical Umpolung of C-H Nucleophiles Bearing Three Electron-Withdrawing Groups to Trigger Radical 1,2-Alkylarylations of Allylic Alcohols" . | ADVANCED SYNTHESIS & CATALYSIS (2025) . |
APA | Li, Qibin , Hu, Die , Xu, Kun , Zeng, Chengchu . Electrochemical Umpolung of C-H Nucleophiles Bearing Three Electron-Withdrawing Groups to Trigger Radical 1,2-Alkylarylations of Allylic Alcohols . | ADVANCED SYNTHESIS & CATALYSIS , 2025 . |
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Abstract :
Electrophotochemical ligand-to-metal charge transfer (LMCT) catalysis has contributed to advancing sustainable radical chemistry by exploiting both visible light and electricity as clean energy inputs. Moreover, electrophotochemical LMCT catalysis is not only beneficial for selective activation of metal-bound ligands even in the presence of more electron-rich moieties, but also exhibits high functional group compatibility due to the low operating potentials resulting from the inherent inner-sphere reactivity mode. Here we highlight the advancements in the field of electrophotochemical LMCT catalysis, with an emphasis on the substrate scope, reaction limitations as well as mechanistic insights. At the end of this review, we provide our views on current challenges and future potential opportunities in this emerging field.
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GB/T 7714 | Zhang, Haonan , Wei, Dengchao , Xu, Kun et al. Electrophotochemical ligand-to-metal charge transfer catalysis: an emerging platform for sustainable synthesis [J]. | GREEN CHEMISTRY , 2025 , 27 (13) : 3413-3430 . |
MLA | Zhang, Haonan et al. "Electrophotochemical ligand-to-metal charge transfer catalysis: an emerging platform for sustainable synthesis" . | GREEN CHEMISTRY 27 . 13 (2025) : 3413-3430 . |
APA | Zhang, Haonan , Wei, Dengchao , Xu, Kun , Zeng, Chengchu . Electrophotochemical ligand-to-metal charge transfer catalysis: an emerging platform for sustainable synthesis . | GREEN CHEMISTRY , 2025 , 27 (13) , 3413-3430 . |
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Abstract :
The electro-generation of acyl radicals from both aromatic and aliphatic aldehydes remains an unmet challenge. We provide a solution to this challenge by merging electro-oxidation and a quinuclidine-mediated hydrogen atom transfer strategy. The generation of acyl radicals at decreased applied potentials compared to that of formyl oxidation exhibits excellent functional group compatibility. The electro-generation of acyl radicals from both aromatic and aliphatic aldehydes is a synthetic challenge. We addressed this challenge by merging electro-oxidation and a quinuclidine-mediated HAT strategy.
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GB/T 7714 | Li, Yongmei , Sun, Liangbo , Huang, Shengyang et al. Electrochemical quinuclidine-mediated Minisci-type acylation of N-heterocycles with aldehydes [J]. | CHEMICAL COMMUNICATIONS , 2024 , 60 (48) : 6174-6177 . |
MLA | Li, Yongmei et al. "Electrochemical quinuclidine-mediated Minisci-type acylation of N-heterocycles with aldehydes" . | CHEMICAL COMMUNICATIONS 60 . 48 (2024) : 6174-6177 . |
APA | Li, Yongmei , Sun, Liangbo , Huang, Shengyang , Xu, Kun , Zeng, Cheng-Chu . Electrochemical quinuclidine-mediated Minisci-type acylation of N-heterocycles with aldehydes . | CHEMICAL COMMUNICATIONS , 2024 , 60 (48) , 6174-6177 . |
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GB/T 7714 | Tan, Zhoumei , Xu, Kun , Zeng, Chengchu . Copper-catalyzed C-H bond functionalization enabled by programmed alternating current [J]. | SCIENCE CHINA-CHEMISTRY , 2024 , 68 (1) : 10-11 . |
MLA | Tan, Zhoumei et al. "Copper-catalyzed C-H bond functionalization enabled by programmed alternating current" . | SCIENCE CHINA-CHEMISTRY 68 . 1 (2024) : 10-11 . |
APA | Tan, Zhoumei , Xu, Kun , Zeng, Chengchu . Copper-catalyzed C-H bond functionalization enabled by programmed alternating current . | SCIENCE CHINA-CHEMISTRY , 2024 , 68 (1) , 10-11 . |
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Abstract :
The quinuclidine (Qu)-catalyzed activation of acylhydrazines to afford the corresponding acyl radicals remains an unmet challenge. To address this challenge, we report a synergistic strategy by combining electro-oxidation with Qu-based HAT catalysis. Enabled by this strategy, the electrochemical Minisci acylation of N-heterocycles with acylhydrazines was realized for the first time.
Keyword :
Acyl radical Acyl radical Synthetic electrochemistry Synthetic electrochemistry Acylhydrazine Acylhydrazine Minisci acylation Minisci acylation Quinuclidine Quinuclidine
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GB/T 7714 | Zhang, Haonan , Wang, Dehui , Xu, Kun et al. Quinuclidine-Catalyzed Electrochemical Minisci Acylation of N-Heteroarenes with Acylhydrazines [J]. | CHEMCATCHEM , 2024 . |
MLA | Zhang, Haonan et al. "Quinuclidine-Catalyzed Electrochemical Minisci Acylation of N-Heteroarenes with Acylhydrazines" . | CHEMCATCHEM (2024) . |
APA | Zhang, Haonan , Wang, Dehui , Xu, Kun , Zeng, Chengchu . Quinuclidine-Catalyzed Electrochemical Minisci Acylation of N-Heteroarenes with Acylhydrazines . | CHEMCATCHEM , 2024 . |
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Abstract :
Radical-polar crossover (RPC) reaction bridges the gap between one- and two-electron reactivities, thus providing an ideal solution to overcome the limitations of both radical and polar chemistry. In this manifold, organic electrochemistry provides a uniquely facile strategy to access a diverse array of radical intermediates, thus broadening the chemical space of the RPC concept. This review highlights the synthetic advances in the field of electrochemical RPC reactions since 2020, with an emphasis on the substrate scope, reaction limitation and mechanistic aspect. The related RPC reactions are categorized as net-oxidative, net-reductive, or redox neutral transformations.
Keyword :
alkene functionalization alkene functionalization polar chemistry polar chemistry radical chemistry radical chemistry electrosynthesis electrosynthesis radical-polar crossover radical-polar crossover
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GB/T 7714 | Tan, Zhoumei , Zhang, Haonan , Xu, Kun et al. Electrochemical radical-polar crossover: a radical approach to polar chemistry [J]. | SCIENCE CHINA-CHEMISTRY , 2023 , 67 (2) : 450-470 . |
MLA | Tan, Zhoumei et al. "Electrochemical radical-polar crossover: a radical approach to polar chemistry" . | SCIENCE CHINA-CHEMISTRY 67 . 2 (2023) : 450-470 . |
APA | Tan, Zhoumei , Zhang, Haonan , Xu, Kun , Zeng, Chengchu . Electrochemical radical-polar crossover: a radical approach to polar chemistry . | SCIENCE CHINA-CHEMISTRY , 2023 , 67 (2) , 450-470 . |
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Abstract :
We report a strategic exploitation of trifluoromethyl thianthrenium triflate (TT-CF3+OTf-) as both electromediator and CF3 radical precursors for paired electrolysis. Enabled by this strategy, the three-component trifluoromethylheteroaromatization of alkenes and alkynes was realized. The superiority of TT-CF3+OTf- to other electrophilic CF3 reagents is attributed to the cathodic generation of thianthrene (TT) as a mediator, which shifts the heterogeneous oxidation of interest to a homogeneous one.
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GB/T 7714 | Xiang, Fang , Wang, Dehui , Xu, Kun et al. Paired Electrolysis Enabled Trifluoromethylheteroaromatization of Alkenes and Alkyne with Trifluoromethyl Thianthrenium Triflate (TT-CF3 +OTf-) as a Bifunctional Reagent [J]. | ORGANIC LETTERS , 2023 , 26 (1) : 411-415 . |
MLA | Xiang, Fang et al. "Paired Electrolysis Enabled Trifluoromethylheteroaromatization of Alkenes and Alkyne with Trifluoromethyl Thianthrenium Triflate (TT-CF3 +OTf-) as a Bifunctional Reagent" . | ORGANIC LETTERS 26 . 1 (2023) : 411-415 . |
APA | Xiang, Fang , Wang, Dehui , Xu, Kun , Zeng, Cheng-Chu . Paired Electrolysis Enabled Trifluoromethylheteroaromatization of Alkenes and Alkyne with Trifluoromethyl Thianthrenium Triflate (TT-CF3 +OTf-) as a Bifunctional Reagent . | ORGANIC LETTERS , 2023 , 26 (1) , 411-415 . |
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Abstract :
The external oxidant-free exploitation of abundant alkane feedstocks as alkyl radical precursors remains a topic of high interest in synthetic communities. Here, we report a Ce-catalyzed electrophotoredox radical addition/cyclization cascade for the incorporation of unactivated alkanes to produce alkylated benzimidazo-fused isoquinolinones and other N-containing polycycles. Compared with previous works employing prefunctionalized alkyl radical precursors, this electrophotocatalytic protocol features high step-economy. The external oxidant-free conditions accompanied by the generation of H2 as the only byproduct further highlight the high redox- and atom-economy of this catalytic protocol. (c) 2022 Elsevier Inc. All rights reserved.
Keyword :
Unactivated alkane Unactivated alkane Cerium catalysis Cerium catalysis Organic electrosynthesis Organic electrosynthesis LMCT LMCT Electrophotocatalysis Electrophotocatalysis
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GB/T 7714 | Tan, Zhoumei , Jiang, Yangye , Xu, Kun et al. Electrophotoredox/cerium-catalyzed unactivated alkanes activation for the sustainable synthesis of alkylated benzimidazo-fused isoquinolinones [J]. | JOURNAL OF CATALYSIS , 2023 , 417 : 473-480 . |
MLA | Tan, Zhoumei et al. "Electrophotoredox/cerium-catalyzed unactivated alkanes activation for the sustainable synthesis of alkylated benzimidazo-fused isoquinolinones" . | JOURNAL OF CATALYSIS 417 (2023) : 473-480 . |
APA | Tan, Zhoumei , Jiang, Yangye , Xu, Kun , Zeng, Chengchu . Electrophotoredox/cerium-catalyzed unactivated alkanes activation for the sustainable synthesis of alkylated benzimidazo-fused isoquinolinones . | JOURNAL OF CATALYSIS , 2023 , 417 , 473-480 . |
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Abstract :
An electrochemical approach for the Minisci-type acylation of quinoxalines with a-keto acids as the acyl radical precursors is reported. With the assistance of TFA as the key additive, acylated quinoxalines were constructed in synthetically useful yields. The distinguishable features of this electrochemical protocol include catalyst-and external oxidant-free conditions, and operational simplicity.
Keyword :
acyl radical acyl radical anodic oxidation anodic oxidation Minisci reaction Minisci reaction & alpha;-keto acids & alpha;-keto acids electrosynthesis electrosynthesis
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GB/T 7714 | Li, Yongmei , Liang, Sen , Wang, Dehui et al. Electrochemical Decarboxylative Minisci-Type Acylation of Quinoxalines under Catalyst- and External-Oxidant-Free Conditions [J]. | SYNTHESIS-STUTTGART , 2023 , 55 (18) : 3026-3032 . |
MLA | Li, Yongmei et al. "Electrochemical Decarboxylative Minisci-Type Acylation of Quinoxalines under Catalyst- and External-Oxidant-Free Conditions" . | SYNTHESIS-STUTTGART 55 . 18 (2023) : 3026-3032 . |
APA | Li, Yongmei , Liang, Sen , Wang, Dehui , Xu, Kun , Zeng, Chengchu . Electrochemical Decarboxylative Minisci-Type Acylation of Quinoxalines under Catalyst- and External-Oxidant-Free Conditions . | SYNTHESIS-STUTTGART , 2023 , 55 (18) , 3026-3032 . |
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