Article
Chemistry, Multidisciplinary
Saira Hafeez, Aamer Saeed
Summary: Visible light-induced acylation of heteroaromatic compounds is achieved using benzoyl hydrazides as an efficient acyl source under mild reaction conditions. The photo-redox catalyzed oxidative cleavage of hydrazides leads to in situ formation of acyl radicals, which subsequently couple with various N-heterocycles to produce acylated products. This synthetic strategy performs the classic Minisci reaction in an eco-friendly and greener way with functional group tolerance and regioselectivity. Control experiments confirm the radical pathway for this transformation.
Article
Chemistry, Organic
Xiang Gu, Taoyong Wang, KaKing Yan
Summary: An environmentally friendly C-H alkylation method of N-heteroarenes facilitated by mechanochemistry is described. Mechanoradicals generated from persulfate via in situ homolysis in the solid state can readily transform alkyl trifluoroborate salts to carbon-based radicals for subsequent C-C bond formation with N-heterocycles.
Article
Chemistry, Organic
Chaodong Wang, Shengjie Song, Zhi Chen, Dengjian Shen, Zhenhui Wang, Jiadi Zhou, Jingjing Guo, Jianjun Li
Summary: In this study, a visible-light-triggered photocatalyst-free radical cascade Minisci reaction was developed for the synthesis of diverse fi-C(sp3) heteroarylated alcohols/ethers using heteroarenes, alkenes, and water/alcohols. This protocol is mild, scalable, and demonstrates broad substrate scope and functional group tolerance. Mechanistic studies reveal that heteroarenes can serve as photocatalysts for single-electron transfer with persulfate.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Tatsuhiro Uchikura, Kazushi Tsubono, Yurina Hara, Takahiko Akiyama
Summary: This study reports a dual-role EDA-SET/HAT photoreaction system for carbon-carbon bond formation using a phenol catalyst and aryl iodide. Irradiation of the EDA complex with visible light generates an aryl radical, which abstracts a hydrogen atom from an sp3 carbon to form an alkyl radical.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Chunlian Wang, Hang Shi, Guo-Jun Deng, Huawen Huang
Summary: In this study, a visible-light-induced photoredox Minisci alkylation reaction of N-heteroarenes with ethyl acetate was successfully achieved. The low-toxic ethyl acetate was employed as the alkylation reagent for the first time, leading to smooth reactions of 4-quinazolinones, quinolines, and pyridines. Mechanistic studies revealed that LiBr significantly enhanced the efficiency of the reaction through mediating hydrogen atom transfer.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Elisabetta Rosadoni, Elena Bombonato, Antonio Del Vecchio, Sara Guariento, Paolo Ronchi, Fabio Bellina
Summary: This note discusses the application of a Minisci-type reaction for the direct alkylation of azoles with carboxylic acids as radical precursors. Different reaction conditions were investigated to achieve high yield of the desired products, focusing on acid strength and solvent screening. Moreover, the reactivity of imidazoles with various carboxylic acids was investigated, showing good yield for most cases. The study reveals the potential of this approach for late-stage functionalization in drug discovery.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Xinxin Wang, Xin Shao, Zhu Cao, Xinxin Wu, Chen Zhu
Summary: A metal-free deformylative Minisci-type reaction is developed using aliphatic aldehydes as alkyl radical precursors. The reaction proceeds through a sequence of hydrogen atom abstraction (HAA) from the aldehyde and decarbonylation under mild photochemical conditions. It offers advantages such as good regioselectivity, broad substrate scope, and easy operation. The reaction is also suitable for late-stage functionalization of complex heteroarenes and can be easily scaled up.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Jiadi Zhou, Quanlei Ren, Ning Xu, Chaodong Wang, Shengjie Song, Zhi Chen, Jianjun Li
Summary: A versatile C(sp(2))-C(sp(3)) bond formation catalyzed by K2S2O8 with N-heteroaromatics and gamma-lactams/amides has been developed. The reaction proceeds in moderate to good yields with high regioselectivity under visible-light-induced photocatalyst-free conditions in H2O at ambient temperature. The new K2S2O8 catalytic mechanism was investigated through control experiments.
Review
Chemistry, Organic
Jianyang Dong, Yuxiu Liu, Qingmin Wang
Summary: N-Heteroarenes are widely present in natural products, small-molecule drugs, organic materials, and ligands, making selective C-H functionalization methods highly sought-after. The Minisci reaction is a useful tool for synthesizing alkyl-substituted nitrogen-containing aromatic rings, and the recent development of photocatalytic Minisci reactions has expanded their scope, successfully applied in drug synthesis.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Roberto del Rio-Rodriguez, Lorena Fragoso-Jarillo, Alberto F. Garrido-Castro, M. Carmen Maestro, Jose A. Fernandez-Salas, Jose Aleman
Summary: We report a general, facile, and environmentally friendly electrochemical method for the Minisci-type alkylation of N-heteroarenes using widely available alkyl halides as radical precursors. The method efficiently generates primary, secondary, and tertiary alkyl radicals, which can be coupled with a variety of N-heteroarenes. The method demonstrates high functional group tolerance and has been applied in the synthesis of biologically valuable building blocks.
Article
Chemistry, Organic
Zhong-Xuan Qiu, Pei-Zhen Dong, Huai-Li Zhao, Mei-Fa Zhao, Bin Qiu, Jian Xiao
Summary: A Bronsted acid-catalyzed direct C(sp(2))-H alkylation method was developed for the synthesis of alkyl-substituted heteroaromatic compounds via cross-dehydrogenative coupling with cyclic ethers in the presence of benzoyl peroxide, achieving yields up to 94% under metal-free conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Serena Pillitteri, Prabhat Ranjan, Gerardo M. Ojeda-Carralero, Laura Y. Vazquez Amaya, Javier E. Alfonso-Ramos, Erik V. van der Eycken, Upendra K. Sharma
Summary: The visible-light promoted photoredox-cobalt catalyzed Minisci reaction allows for mild cross-coupling reactions using various boronic acids and derivatives as alkyl radical precursors. This reaction has high efficiency, good selectivity, and broad applicability for different N-heteroarenes.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Youjung Byun, Junghyea Moon, Won An, Neeraj Kumar Mishra, Hyung Sik Kim, Prithwish Ghosh, In Su Kim
Summary: The study focuses on the transition-metal-free alkylation and acylation of C(sp(2))-H bonds in biologically relevant 2-benzoxazinones using 1,4-dihydropyridines as radical surrogates. The research demonstrates excellent functional group compatibility and a broad substrate scope. Additionally, gram-scale reaction and transformations of the synthesized adducts via Suzuki coupling with heteroaryl boronic acids highlights the synthetic potential of the developed protocol.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Jianyang Dong, Fuyang Yue, Jianhua Liu, Hongjian Song, Yuxiu Liu, Qingmin Wang
Summary: The described Minisci reaction allows for the catalytic synthesis of heteroarylethyl alcohols by sequentially adding H2O and N-heteroarenes across olefinic double bonds. This scalable protocol enables direct hydroxy-heteroarylation of olefins with a wide range of N-heteroarenes and has the potential to rapidly convert abundant feedstock materials into medically relevant molecules.
Article
Chemistry, Organic
Jorge C. Herrera-Luna, David Diaz Diaz, Alex Abramov, Susana Encinas, M. Consuelo Jimenez, Raul Perez-Ruiz
Summary: In this study, the borylation of heteroarene boronate esters was achieved under very mild conditions in an easy-to-use gel nanoreactor, using visible light as the energy source at room temperature in photocatalyst-free and aerobic conditions. The gel network provided a stabilizing microenvironment to support a wide substrate scope, making this protocol attractive for the synthesis of new materials.
Article
Chemistry, Multidisciplinary
Jianyang Dong, Andreas Ostertag, Christof Sparr
Summary: In this study, the accessibility of atropisomeric o-quinodimethanes and the enantioselective synthesis of their precursors were described. The catalyst-stereocontrolled [2+2+2] cycloaddition and subsequent stereospecific Diels-Alder reactions enabled the synthesis of enantioselective compounds with high selectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Biochemistry & Molecular Biology
Lili Li, Rongxin Yang, Jianhua Liu, Jingjing Zhang, Hongjian Song, Yuxiu Liu, Qingmin Wang
Summary: Based on widely used drug design scaffolds, novel tryptophan derivatives with antiviral and antifungal activities were synthesized. Some of these compounds also exhibited larvicidal activities against certain pest species.
Article
Chemistry, Multidisciplinary
Pan Zhou, Haoran Jiao, Kaikai Niu, Hongjian Song, Yuxiu Liu, Qingmin Wang
Summary: This article reports an electrochemical diselenylation method for terminal alkynes, obtaining trisubstituted alkenes in an antiselective manner with 100% atom economy. This green technology uses simple graphite electrodes and MeCN as solvent, without requiring high temperatures, resulting in high regioselectivity for trisubstituted alkenes. The successful gram-scale reaction, tolerance to multiple functional groups, and functionalization of complex compounds highlight the importance of this method.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Organic
Xiaodi Shi, Yunpeng Cao, Yuxiu Liu, Kaikai Niu, Hongjian Song, Jingjing Zhang, Qingmin Wang
Summary: Direct functionalization of C(sp(3))-H bonds is a useful method for obtaining a variety of heteroarene derivatives. However, its application is limited by the need for catalysts or oxidants. In this study, a mild and eco-friendly photochemical protocol was developed for decarbonylative C-H alkylation reactions using quinoxalin-2(1H)-ones and aliphatic aldehydes with air as the oxidant at room temperature. These catalyst- and oxidant-free reactions exhibited good functional group tolerance and a wide substrate scope.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Biochemistry & Molecular Biology
Kaihua Wang, Beibei Wang, Henan Ma, Ziwen Wang, Yuxiu Liu, Qingmin Wang
Summary: Plant diseases and insect pests can have significant negative effects on crop yield and quality, making them difficult to control. This study focuses on the discovery of new pesticides from natural products. By selecting the naphthoquinones plumbagin and juglone as parent structures, a series of their derivatives were designed, synthesized, and evaluated for their activities against fungi, viruses, and insects. The naphthoquinones demonstrated broad-spectrum antifungal activities against various types of fungi and some compounds showed superior fungicidal activities compared to pyrimethanil. Certain compounds also exhibited potent antiviral activities against the tobacco mosaic virus. Additionally, some of the compounds displayed excellent insecticidal activities. This research provides a foundation for the application of plumbagin and juglone in plant protection.
Article
Biochemistry & Molecular Biology
Wanjun Ni, Hongjian Song, Lizhong Wang, Yuxiu Liu, Qingmin Wang
Summary: Compounds with acylhydrazone fragments, containing amide and imine groups, exhibit significant biological activity due to their ability to act as electron donors and acceptors, making them easier to bind to biological targets. In this study, acylhydrazone fragments were introduced to matrine, a natural alkaloid, in order to enhance its biological activity. The synthesized compounds showed excellent anti-virus activity against the tobacco mosaic virus (TMV) and also demonstrated insecticidal and fungicidal activities against diamondback moth and mosquito larvae.
Article
Biochemistry & Molecular Biology
Yongyue Gao, Xingxing He, Lili Yan, Hongyu Zhang, Sijia Liu, Qian Ma, Peiyao Zhang, Yan Zhang, Zijun Zhang, Ziwen Wang, Aidang Lu, Qingmin Wang
Summary: Pesticides are crucial for agricultural development, and the development of green, safe, and efficient pesticides is urgent. Bisindole alkaloids, with their unique and concise structures and broad biological activities, play an important role in the creation of new pesticides. In this study, bisindole alkaloid barakacin and its derivatives were synthesized and evaluated for their antiviral and antifungal activities. Compound 14b exhibited superior antiviral activity against tobacco mosaic virus (TMV) and could potentially serve as a novel antiviral candidate.
Article
Multidisciplinary Sciences
Xiaochen Wang, Rongxin Yang, Binbing Zhu, Yuxiu Liu, Hongjian Song, Jianyang Dong, Qingmin Wang
Summary: Here, the authors describe a multicatalytic method for the synthesis of beta, gamma-unsaturated ketones via allylic acylation of alkenes. The method combines N-heterocyclic carbene catalysis, hydrogen atom transfer catalysis, and photoredox catalysis for cross-coupling reactions. The method shows excellent site selectivity and could be used for the synthesis of diverse beta, gamma-unsaturated ketones using carboxylic acids and olefins as substrates.
NATURE COMMUNICATIONS
(2023)
Article
Agriculture, Multidisciplinary
Wentao Xu, Rongxin Yang, Lixia Liu, Jingjing Zhang, Yuxiu Liu, Yongqiang Li, Lizhong Wang, Hongjian Song, Qingmin Wang
Summary: Marine natural products have become increasingly important in drug research and development because of their unique structure, diverse biological activities, and novel mode of action. This study focused on designing and synthesizing derivatives of antiviral alkaloidal disine by introducing hydrogen-bond receptors or donors into molecules. The derivatives exhibited antiviral activity against tobacco mosaic virus (TMV), with some compounds showing better activity than the commercial antiviral drug ribavirin. Additionally, the derivatives demonstrated larvicidal and broad-spectrum fungicidal activities, making them potential candidates for further investigation.
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
(2023)
Article
Agriculture, Multidisciplinary
Yubin Xu, Xin Guo, Tingyi Li, Taiqing Li, Xin Ding, Ziwen Wang, Aidang Lu, Qingmin Wang
Summary: Plant pathogenic fungi and viruses pose a serious threat to agricultural production. This study focused on designing and synthesizing laurene derivatives and evaluating their antiviral and fungicidal activities. Compound 11a demonstrated promising antiviral activity and presented a simple chemical structure, making it a potential candidate for further development.
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Pan Zhou, Senhui Wu, Kaikai Niu, Hongjian Song, Yuxiu Liu, Jingjing Zhang, Qingmin Wang
Summary: A novel method for the synthesis of quindoline derivatives using intramolecular ring-closure reactions and an iminium salt intermediate has been developed. This method offers the advantages of short reaction time, operational simplicity, and nearly quantitative yields, making it suitable for the rapid synthesis of valuable quindoline derivatives.
CHEMICAL COMMUNICATIONS
(2023)
Review
Chemistry, Multidisciplinary
Xiaochen Wang, Senhui Wu, Rongxin Yang, Hongjian Song, Yuxiu Liu, Qingmin Wang
Summary: N-Heterocyclic carbenes (NHCs) are Lewis basic catalysts that can mediate organic transformations through polarity reversal. Recent advances have combined NHC catalysis with photoredox catalysis to enable NHC-mediated radical reactions under mild conditions. This review focuses on elucidating the mechanisms and exploring the opportunities and challenges of combining photoredox and NHC catalysis.
