Article
Chemistry, Organic
Lian Xue, Xia Song, Xinying Zhang, Xuesen Fan
Summary: An effective and sustainable synthesis of O-heterocycle spiro-fused cyclopentaquinolinone and cyclopentaindene derivatives has been presented through light-driven cascade reactions. The reactions are initiated by visible light-induced radical formation from O-heterocycle, followed by regioselective addition onto acrylamide or acrylate moiety and cascade radical annulation. The newly developed protocol has advantages including broad substrate scope, mild reaction conditions, excellent atom-economy, high efficiency, and good compatibility with diverse functional groups.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Akira Matsumoto, Bich-Ngoc Nguyen, Tsubasa Honda, Ryu Sakamoto, Xiao Huang, Shigeyoshi Sakaki, Keiji Maruoka
Summary: This article discusses the synthetic application of ketone-derived oxaziridines as alkyl radical precursors in copper-catalyzed Carbon-Carbon bond formation reactions. Experimental and computational studies show an efficient generation of alkyl radicals through a free radical mechanism. Acyclic and unstrained cyclic oxaziridines are applicable, allowing for the generation of various alkyl radicals with good functional group compatibility.
CHEMISTRY-AN ASIAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Airi Kuroda, Naoko Fujita, Tomomi Horita, Kei Ota, Alfredo Rosas-Sanchez, Manabu Hoshino, Daisuke Hashizume, Tsukasa Matsuo
Summary: In this study, the reaction between the bulky EMind-based compound and pyridine N-oxide was investigated, resulting in the formation of different germanium compounds. The reaction mechanism was also explored.
Article
Chemistry, Applied
Sofia Strekalova, Alexander Kononov, Vladimir Morozov, Olga Babaeva, Elena Gavrilova, Yulia Budnikova
Summary: This study describes the electrochemical amidation of C(sp2)-H and C(sp3)-H bonds of a wide range of arenes using nitriles as amide sources, achieved under mild conditions without the need for metal catalysts or external oxidizing agents. The method offers moderate to high yields, can be applied to arenes with diverse functional groups, and is suitable for gram scale synthesis. The key role of the hydroxyl radical as an inductor generated during the oxidation of water has been established through EPR experiments.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Review
Chemistry, Organic
Biprajit Paul, Hrishikesh Paul, Indranil Chatterjee
Summary: This review highlights the development of photoredox-mediated desulfonylation reactions since 2000, which have emerged as a powerful strategy for C-C and C-X bond formation. The mild reaction conditions, wide functional group tolerance, and excellent synthetic efficacy make these reactions highly attractive in synthetic organic, bio, and material chemistry.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Muhammad Asif Iqbal, Le Lu, Hina Mehmood, Ruimao Hua
Summary: This study reports a Cs2CO3-promoted cross-coupling reaction of arenes with cyano-/nitro-substituted aryl halides in DMSO to afford biaryls in the absence of ligands. The cyano/nitro groups in biaryls are shown to be useful for further transformations. Additionally, the formation of dibenzofurans from reactions between arenes and 1-bromo-2-iodobenzene is reported. A radical mechanism for the formation of biaryls is proposed based on control experiments and theoretical studies.
Article
Chemistry, Organic
Ganesh Pandey, Sandip Kumar Tiwari, Pushpendra Singh, Pradip Kumar Mondal
Summary: The photocatalytic regiospecific p-silylation of arenes has been achieved through the coupling of in situ generated silyl radical with arene radical cation. The p-silylated arenes can be further utilized for exclusive o-silylation reaction, regiospecific o-acylation, and o-alkylation reaction.
Article
Chemistry, Multidisciplinary
Kisturi Dhanwant, Aarti Saini, Tristram Chivers, Ramalingam Thirumoorthi
Summary: The oxidative-addition reaction between an arylmethyl chloride and tin powder produces bis(arylmethyl)tin dichlorides in good yields. Decomposition of bis(1-naphthylmethyl)tin dichloride at 160 degrees C generates 1-naphthylmethyl radicals which can be utilized for efficient substitution reactions to obtain unsymmetrical diarylmethanes. The addition of iodine to the reaction mixture increases the yields of coupled products significantly.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Applied
Weidi Zeng, Linyong Li, Chihao Wang, Duozhi Wang, Lei Zhou
Summary: A relay photocatalytic cascade reaction was developed for the synthesis of 3-amino-1-(difluoromethylidene)tetralins. The reaction utilized readily available starting materials and combined two photoredox catalytic cycles with a single photocatalyst. The method allows for the construction of various 3-amino-tetralins bearing an exo-difluoroethylene unit in good yields.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Claire Empel, Thanh Vinh Nguyen, Rene M. Koenigs
Summary: In this study, a nonbenzenoid aromatic carbocation, tropylium, was utilized as an organic Lewis acid catalyst in O-H functionalization reactions of diazoalkanes with benzoic acids, showing excellent efficiency across a wide range of substrates.
Article
Chemistry, Physical
Mamiko Hayakawa, Hisashi Shirota, Souta Hirayama, Ryuusei Yamada, Tadashi Aoyama, Akihiko Ouchi
Summary: Sunlight-induced C-C bond formation reactions with di-tert-butyl peroxide showed higher yields and faster reaction rates compared to conventional Xe lamp photolysis, especially with olefins bearing two EWGs. Gram-scale experiments demonstrated similar yields to small-scale experiments.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2021)
Article
Chemistry, Physical
Yaxuan Jing, Mohsen Shakouri, Xiaohui Liu, Yongfeng Hu, Yong Guo, Yanqin Wang
Summary: Researchers have developed a strategy to selectively cleave C-C bonds in aromatic plastics using catalyst Ru/Nb2O5 through methanol poisoning, resulting in monocyclic phenolic compounds.
Article
Chemistry, Physical
Ralf Kaiser, Long Zhao, Wenchao Lu, Musahid Ahmed, Marsel Zagidullin, Valeriy N. Azyazov, Alexander M. Mebel
Summary: Resonantly stabilized free radicals are considered fundamental molecular building blocks in the formation of polycyclic aromatic hydrocarbons and carbonaceous nanoparticles. Research has shown the formation of benzene and naphthalene through specific reactions at elevated temperatures, providing important insights into organic hydrocarbon chemistry in high temperature circumstellar environments and combustion systems.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Review
Chemistry, Organic
Li Cheng, Quan Lin, Yunrong Chen, Hegui Gong
Summary: This review summarizes the recent developments on thermo-driven C(sp(3))-O bond radical scission methods and their applications in constructing C(sp(3))-C bonds. The focus is on the generation and transformation of radical intermediates under different approaches.
SYNTHESIS-STUTTGART
(2022)
Review
Chemistry, Organic
Dan-Hong Wan, Hai-Bin Yang
Summary: NHC-catalyzed radical cross-coupling reactions provide an efficient method for accessing ketones by reacting with sp(3)-hybridized carbon radical precursors. This reaction indirectly overcomes the limitations in the scope of coupling partners in NHC umpolung catalyzed reactions of aldehydes.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Hao Wan, Dongting Li, Huadan Xia, Liwen Yang, Hesham Alhumade, Hong Yi, Aiwen Lei
Summary: Efficient and sustainable C-N bond-forming reactions to N-heterocyclic frameworks have been a long-standing interest in organic synthesis, and in this work, a new electrochemical radical C-sp2-H/N-H cyclization method to synthesize 1H-indazoles was developed. The use of HFIP as a solvent or proton donor, along with its ability to promote the formation of N free radicals, was key in the success of this synthetic methodology.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Mingming Yu, Yuhan Gao, Lin Zhang, Yingjie Zhang, Yiyan Zhang, Hong Yi, Zhiliang Huang, Aiwen Lei
Summary: A novel electrochemical strategy is proposed to selectively and sustainably synthesize isoindolinones using simple o-alkyl benzoic acids and nitriles as substrates under metal catalyst and external oxidant-free conditions. The protocol exhibits good functional group tolerance and the nitrile plays a vital role in constructing the amide bond in the product.
Article
Chemistry, Multidisciplinary
He Zhang, Shengchun Wang, Xiaoyu Wang, Pengjie Wang, Hong Yi, Heng Zhang, Aiwen Lei
Summary: By utilizing inexpensive K2S2O8 as the oxidant at room temperature, the phenoxazination/phenothiazination of electron-rich anilines has been successfully achieved. This catalyst-free method demonstrates complete para-selective amination, showing high efficiency and simplicity in flow-chemistry synthesis.
Article
Chemistry, Multidisciplinary
Yongli Li, Huamin Wang, Zhuning Wang, Hesham Alhumade, Zhiliang Huang, Aiwen Lei
Summary: This article describes a method for selectively activating C(sp(3))-S bonds, which is achieved through a radical-mediated electrochemical strategy for the synthesis of valuable disulfides from thioethers. The method features mild reaction conditions and excellent chemoselectivity.
Article
Chemistry, Organic
Jianguo Hu, Shengchun Wang, Bin Li, Aiwen Lei
Summary: We report a protocol for constructing tetrahydroquinolines from bulk chemicals (alkenes and anilines) induced by K2S2O8. The method exhibits operational simplicity, wide scope, mild conditions, and a transition-metal-free system.
Article
Chemistry, Organic
Chang-Ming You, Cheng Huang, Sheng Tang, Peng Xiao, Shengchun Wang, Zhenhong Wei, Aiwen Lei, Hu Cai
Summary: Direct N-allylation of azoles with hydrogen evolution has been achieved by the synergistic combination of organic photocatalysis and cobalt catalysis. This protocol eliminates the need for stoichiometric oxidants and prefunctionalization of alkenes, and produces hydrogen (H2) as a byproduct. The transformation highlights high step and atom economy, high efficiency, and broad functional group tolerance, opening up a pathway for valuable C-N bond formation in heterocyclic chemistry.
Article
Multidisciplinary Sciences
Dongfeng Yang, Zhipeng Guan, Yanan Peng, Shuxiang Zhu, Pengjie Wang, Zhiliang Huang, Hesham Alhumade, Dong Gu, Hong Yi, Aiwen Lei
Summary: By electrochemical oxidative difunctionalization, the authors achieved functionalization of diazo compounds with two different nucleophiles. This method allows the synthesis of structurally diverse heteroatom-containing compounds, which are difficult to access by traditional methods, and display important synthetic applications. The reaction conditions are mild, exhibiting excellent functional group tolerance and efficiency for large-scale synthesis.
NATURE COMMUNICATIONS
(2023)
Editorial Material
Chemistry, Physical
Shengchun Wang, Aiwen Lei
Summary: A detailed mechanistic picture of electron transfer in polypyridine nickel systems has been reported, providing an answer to the challenging puzzle of electron transfer in these complexes.
Review
Chemistry, Multidisciplinary
Wuyin Wang, Wentao Mo, Zishan Hang, Yueying Huang, Hong Yi, Zhijun Sun, Aiwen Lei
Summary: Transition metal element, copper, plays diverse and pivotal roles in oncology. It acts as constituents of metalloenzymes involved in cellular metabolism, function as signaling molecules to regulate the proliferation and metastasis of tumors, and are integral components of metal-based anticancer drugs. Notably, recent research reveals that excessive copper can also modulate the occurrence of programmed cell death (PCD), known as cuprotosis, in cancer cells.
Review
Chemistry, Multidisciplinary
Li Zeng, Jianxing Wang, Daoxin Wang, Hong Yi, Aiwen Lei
Summary: Organic electrosynthesis using alternating current (AC) is still in its early stages due to the lack of a comprehensive theoretical framework. This article provides an overview of recent advancements in AC-driven organic transformations and explores the differences between DC and AC electrolytic methodologies based on their physical principles. These differences include the prevention of metal catalyst deposition, precise modulation of oxidation and reduction intensities, and mitigation of mass transfer processes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Xingchen Liu, Haohua Chen, Dali Yang, Binjing Hu, Ying Hu, Shengchun Wang, Yu Lan, Aiwen Lei, Jie Li
Summary: A multicomponent sulfonylation reaction using sulfonyl chlorides and OPiv-supported organozinc reagents was achieved via cobalt-catalyzed alkene difunctionalizations. Anion-coordination played a critical role in modifying the reactivity and chemical properties of organozinc reagents. The OPiv-coordination resulted in the lower reducibility of arylzinc pivalates, allowing for the in situ formation of catalytically relevant Co(I) species as the active catalyst in carbosulfonylation reactions.
Article
Chemistry, Multidisciplinary
Jinming Wang, Yichang Liu, Xupeng Zong, Aiwen Lei, Zaicheng Sun
Summary: Photochemistry has become increasingly important in organic synthesis and heterogeneous photocatalysts have advantages over traditional homogeneous photocatalysts in terms of production, separation, catalyst recycling, and stability. In this review, the development and advantages of a heterogeneous catalytic system for C-N bond formation as a typical coupling reaction are summarized. Important heterogeneous photocatalysts such as titanium dioxide, semiconductor quantum dots, covalent organic frameworks, and carbon nitrides are discussed in detail. The combination and electron transfer pathway between heterogeneous catalysts and transition-metal catalysts are the focus of this review. These advances not only apply to C-N coupling, but also extend to other coupling reactions.
Article
Chemistry, Multidisciplinary
Yiran Xu, Shengchun Wang, Zhao Liu, Mian Guo, Aiwen Lei
Summary: A photo/nickel dual-catalyzed defluorinative sulfonylation method has been developed to synthesize gem-difluoro allylsulfones rapidly and reliably. This protocol demonstrates mild conditions and a wide scope, providing a novel strategy for the sulfonyl radical participating in radical defluorinative coupling.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Zhipeng Guan, Yanan Peng, Dongfeng Yang, Shuxiang Zhu, Heng Zhang, Aiwen Lei
Summary: A novel electrochemical oxidative four-component reaction for the synthesis of alpha-amino amides via C(sp(3))-H bond activation is reported. The reaction can be carried out on a large scale under metal-free and external oxidant-free conditions, showing good functional group tolerance.
Article
Chemistry, Organic
Hao Li, Fangling Lu, Jie Xu, Jianguo Hu, Hesham Alhumade, Lijun Lu, Aiwen Lei
Summary: Organoselenium compounds are important in medicinal chemistry, materials chemistry, and biochemistry. The selenation of pharmaceutical molecules is a promising method for discovering new drugs. This study introduces an electrochemical oxidative radical cascade cyclization of olefinic amides and diselenides without the need for transition-metal catalysts and external oxidants, resulting in high yields of desired products.
ORGANIC CHEMISTRY FRONTIERS
(2022)
