Article
Chemistry, Multidisciplinary
Dingyi Wang, Binbin Yuan, Jiawei Xu, Lutz Ackermann
Summary: In this study, an electrochemical strategy was used to achieve the dual functionalization of unactivated alkenes through an intramolecular migration process. This strategy eliminated the need for sacrificial chemical oxidants and noble-metal catalysts, and the reactions were carried out under mild conditions. The electrochemistry enabled the migration of (hetero)aryl groups, leading to the formation of alkenyl/alkynyl-migration products. The reaction mechanism was established through experiments and computations.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Organic
Jing-Hao Qin, Ning Nan, Jin-Heng Li
Summary: The electrochemical alkene difunctionalization reaction is an efficient and sustainable method for constructing vicinal difunctionalized structures in organic synthesis. It eliminates the need for additional redox catalysts, metal catalysts, or chemical oxidants and avoids the generation of chemical waste by solely using electrons as the redox agents. This review summarizes the recent advancements in electrochemical alkene difunctionalization, focusing on reaction features, scope, limitations, and mechanistic rationalizations of three categories of alkene difunctionalization methods: nucleophile-terminated, radical-terminated, and functionality migration-terminated reactions.
SYNTHESIS-STUTTGART
(2023)
Review
Chemistry, Applied
Liguo Lu, Dayun Huang, Zefeng Wang, Xingyong Wang, Xiangmei Wu
Summary: Alkenes are valuable in organic synthesis, and they can be easily transformed into selenium or sulfur-containing compounds with a neighboring functional group via three-component reactions. This approach reduces the number of steps and waste generation while enabling the formation of complex molecules from simple starting materials. Recent developments in selenylation and thiolation reactions are summarized in this review, including various reactants such as electron-rich arenes, alcohols, water, acids, and other compounds. This review aims to provide insights for future research in this area.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Review
Chemistry, Applied
Shintaro Kawamura, Pablo Barrio, Santos Fustero, Jorge Escorihuela, Jianlin Han, Vadim A. Soloshonok, Mikiko Sodeoka
Summary: The difunctionalizative trifluoromethylation of unsaturated C-C bonds is a highly useful and efficient method for synthesizing trifluoromethyl compounds. This review focuses on reactions that simultaneously form C-heteroatom and C-H bonds, providing useful CF3 group-containing building blocks. The comprehensive survey categorizes reactions into those that are synthetically mature and those with room for further development.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Subrata Patra, Ivan Mosiagin, Rahul Giri, Thomas Nauser, Dmitry Katayev
Summary: This paper introduces an electrochemically assisted method for generating nitryl radicals from ferric nitrate using inexpensive graphite and stainless-steel electrodes under mild reaction conditions. The reaction mechanism is supported by spectroscopic and experimental studies. The synthesis of diverse products is demonstrated through the development of highly efficient nitration protocols for various unsaturated hydrocarbons. These protocols have broad applications, are easily scalable for large quantities, and exhibit exceptional substrate generality and functional-group compatibility.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jixin Wang, Donghao Luo, Ying Hu, Zhili Duan, Jianlin Yao, Konstantin Karaghiosoff, Jie Li
Summary: Simultaneous formation of carbon-carbon and carbon-heteroatom bonds through transition metal-catalyzed alkene difunctionalization is a powerful tool for synthetic organic chemistry. A new type of S- and P-stabilized bromoallenes for palladium-catalyzed modular allenation and borylation of alkenes has been developed, enabling the synthesis of multiply functionalized allenes in a highly selective manner. This method offers broad substrate scope and functional group compatibility, allowing for the facile installation of allenyl and boryl groups across alkenes.
SCIENCE CHINA-CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Jie Huang, Zhi-Min Chen
Summary: The alkynylative difunctionalization of alkenes is an important synthetic method and has made significant progress in recent years. This review provides a comprehensive summary of this reaction, including alkynylation-initiated and alkynylation-terminated difunctionalizations of alkenes.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Min Ji Kim, Diana J. Wang, Karina Targos, Uriel A. Garcia, Alison F. Harris, Ilia A. Guzei, Zachary K. Wickens
Summary: We have developed a new method for the synthesis of cyclopropanes using abundant carbon pronucleophiles and unactivated alkenes. This scalable protocol exhibits high diastereoselectivity and tolerates diverse functional groups on both coupling partners.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yunlong Wei, Hong Zhang, Xinxin Wu, Chen Zhu
Summary: The radical-mediated difunctionalization of alkenes introduces one alkenyl or alkynyl group to target compounds, but simultaneous installation of two unsaturated C-C bonds via alkene difunctionalization remains challenging due to the high instability of alkenyl and alkynyl radicals. This study reports the successful photocatalytic 1,2-alkynylalkenylation and 1,2-enynylalkenylation of alkenes, utilizing stabilized allenyl radicals for intermolecular addition, with a broad substrate scope and increased degree of unsaturation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Shenghan Teng, Yonggui Robin Chi, Jianrong Steve Zhou
Summary: Asymmetric coupling efficiently occurs between propargylic acetates, cycloalkenes, and electron-rich heteroarenes, yielding 2,3-disubstituted tetrahydrofurans and pyrrolidines in trans configuration with excellent enantiomeric ratios. The reaction proceeds via Wacker-type attack of nucleophilic heteroarenes on alkenes activated by allenyl Pd-II species.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Yi-qun Qin, De Chen, Liang Liu, Jia-jia Zhang, Xin-ju Peng, Yong-yue Luo, Wei Deng, Jiannan Xiang
Summary: The metal-free oxidative alkene methylation/alkynylation reaction using an organic peroxide as the methyl source provides a practical and efficient method for synthesizing challenging quaternary-carbon-containing but-3-yn-1-ones. The reaction exhibits excellent functional group tolerance, broad substrate scope, and exquisite selectivity.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Multidisciplinary
An-Yi Chang, Samar S. Sandhu, P. U. Ashvin I. Fernando, Gilbert. K. Kosgei, Caitlin Bresnahan, Jared S. Cobb, Jose F. Morales, Jiachi Zhou, Shichao Ding, Ashley Hanna, Johanna Jernberg, Joseph Wang
Summary: This study reports a new di-boronic acid-functionalized ferrocene (FDBA) molecular receptor for noncovalent F- recognition, which is used to develop a solid-state miniaturized voltammetric fluoride sensor capable of direct and reversible F- detection in drinking water and community water. The sensing mechanism is based on the conformational change of FDBA facilitated by the unique linkage of two electron-accepting phenylboronic acid moieties with the electron-donating ferrocene moiety. The performance of the sensor is compared to traditional potentiometric F-ISEs, showing significant advantages.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Chemistry, Organic
Kehan Zhou, Chenglei Lv, Niankai Fu
Summary: We describe an efficient and sustainable electrocatalytic method for azidoesterification of alkenes. By using electrochemical iron-catalyzed oxidation of commercially available carbazates, alkoxycarbonyl radicals are generated and added across alkenes to form difunctionalized products. This simple protocol enables the transformation of various alkenes into beta-azido esters with good yields, providing a practical access to beta-amino acid derivatives.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Fengxiang Zhu, Jianxin Xue, Xiao-Feng Wu
Summary: An Fe(II)-catalyzed three-component 1,2-difunctionalization of alkenes with di-tert-butyl peroxide as the methylation reagent has been reported. This method enables 1,2-methylamination and 1,2-methylarylation of various alkenes using nucleophiles such as aromatic amines, pyrrole, and indoles. The simplicity of this protocol allows for the rapid synthesis of complex molecules from simple starting materials.
Article
Chemistry, Organic
Xiang Li, Yong-Liang Tu, Xiang-Yu Chen
Summary: Alkenes are versatile building blocks in organic synthesis, but achieving single-electron reduction is challenging. Photocatalysis has emerged as a promising and efficient tool. This Concept provides an overview of current synthetic techniques for photoinduced single-electron reduction of alkenes.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Hong Yan, Shaobin Zhu, Hai-Chao Xu
Summary: A two-step continuous-flow system was developed for the synthesis of functionalized acridinium photocatalysts through late-stage C(aryl)-H functionalization of the acridinium core, allowing the introduction of a diverse range of alkyl groups and formation of 3,6-disubstituted acridinium dyes.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2021)
Review
Chemistry, Multidisciplinary
Na Chen, Hai-Chao Xu
Summary: Organic radicals, versatile synthetic intermediates with complementary reactivities to ionic species, have limited scope in electrochemically driven reactions; however, research activity in organic electrochemistry has significantly increased in recent years, with the development of methods for generating and utilizing organic radicals for synthesis through direct electrolysis, molecular electrocatalysis, or molecular electrophotocatalysis.
Article
Electrochemistry
Zhong-Wei Hou, Hai-Chao Xu
Summary: An electrophotocatalytic method has been developed for the dehydrogenative cross coupling of arenes with azoles using a bicatalytic system consisting of acridinium dye and (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO). The reactions take place in a simple undivided cell with visible-light irradiation and do not require an external chemical oxidant.
Article
Chemistry, Organic
Yun-Tao Zheng, Jinshuai Song, Hai-Chao Xu
Summary: Indole is commonly found in bioactive compounds and natural products. A new electrocatalytic method has been developed for the synthesis of indoles through dehydrogenative cyclization of 2-vinylanilides, providing a speedy and efficient access to 3-substituted and 2,3-disubstituted indoles without the need for external chemical oxidants.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Multidisciplinary Sciences
Chen-Yan Cai, Zheng-Jian Wu, Ji-Ying Liu, Ming Chen, Jinshuai Song, Hai-Chao Xu
Summary: Oxidative allylic C-H functionalization is a powerful tool in organic synthesis, minimizing the need for functional group activation and generating alkenyl-substituted products amenable to further modifications. The authors introduce an oxidant-free, electrocatalytic approach using tailored cobalt-salen complexes for intramolecular oxidative allylic C-H amination and alkylation, broadening the scope of such reactions.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Ming Chen, Zheng-Jian Wu, Jinshuai Song, Hai-Chao Xu
Summary: In this study, an electrocatalytic allylic C-H alkylation reaction with carbon nucleophiles was achieved using a readily available cobalt-salen complex as the catalyst. The mild conditions and unique electrocatalytic radical process allowed for excellent functional group tolerance and substrate compatibility.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Bin Guo, Hai-Chao Xu
Summary: The electrocatalytic dehydrogenative C(sp3)-H/C(sp)-H cross-coupling of tetrahydroisoquinolines with terminal alkynes has been achieved in a continuous-flow microreactor using TEMPO/copper relay catalysis. The reaction is easily scalable, requires low concentration of supporting electrolyte, and does not need external chemical oxidants or ligands, providing a straightforward and sustainable access to 2-functionalized tetrahydroisoquinolines.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Ya-Long Liu, Xiang-Yue Liu, Li Feng, Lan-Xing Shao, Si-Jun Li, Jing Tang, Hu Cheng, Zhuo Chen, Rui Huang, Hai-Chao Xu, Jin-Liang Zhuang
Summary: Two-dimensional metal-organic nanosheets (2D MONs) are emerging ultrathin, porous, and crystalline materials with advantages such as diversity of organic ligands and metal nodes. They possess high density and accessible catalytic sites, reducing diffusion pathways and enabling fast electron transport. This review summarizes the synthetic methods for fabricating 2D MONs, discusses their applications in electrocatalysis and photocatalysis, and provides insights into future design and synthesis challenges for high-performance applications.
Editorial Material
Chemistry, Organic
Hai-Chao Xu, Kevin D. Moeller
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Liang-Hua Jie, Bin Guo, Jinshuai Song, Hai-Chao Xu
Summary: This study presents an electrocatalytic strategy for the cyclopropanation of active methylene compounds using an organic catalyst, which eliminates the need for transition metal catalysts and external chemical oxidants. The method shows a broad substrate scope and excellent scalability, allowing for the convenient synthesis of various types of cyclopropane-fused heterocyclic and carbocyclic compounds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
Hao Long, Chong Huang, Yun-Tao Zheng, Zhao-Yu Li, Liang-Hua Jie, Jinshuai Song, Shaobin Zhu, Hai-Chao Xu
Summary: The study presents a catalyst- and external oxidant-free continuous flow electrochemical C-H phosphorylation reaction for synthesizing aryl phosphorus compounds. The reaction involves arenes reacting with anodically generated P-radical cations, allowing for efficient reactions of arenes with diverse electronic properties and selective late-stage functionalization of complex natural products and bioactive compounds. The method demonstrates the synthetic utility by producing 55.0 grams of phosphonate product in a continuous manner.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Peng Xiong, Marcel Hemming, Sergei I. Ivlev, Eric Meggers
Summary: Merging electrochemistry with asymmetric catalysis offers a environmentally friendly and efficient strategy for synthesizing nonracemic chiral molecules. This study presents a catalytic asymmetric indirect electrolysis that achieves enantioselective nucleophilic alpha-C(sp(3))-H alkenylation of ketones by employing a combination of a redox mediator and a chiral-at-rhodium Lewis acid. The reaction demonstrates high yields and exceptional enantioselectivities without the need for additional oxidants.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
Hao Long, Tian-Sheng Chen, Jinshuai Song, Shaobin Zhu, Hai-Chao Xu
Summary: The authors report a scalable electrochemical method for the direct hydroxylation of arene C-H bonds in continuous flow, resulting in the synthesis of phenols. This method does not require any catalysts or chemical oxidants, and exhibits excellent selectivity and efficiency, making it applicable to a wide range of arenes. The authors demonstrate the scalability of this method by continuously producing a significant amount of phenol product.
NATURE COMMUNICATIONS
(2022)
Review
Chemistry, Physical
Zhong-Wei Hou, Hai-Chao Xu, Lei Wang
Summary: This review summarizes the recent advances in electrochemical dehydrogenative N-H/N-H coupling reactions, focusing on the mechanistic insights and synthetic applications of these transformations.
CURRENT OPINION IN ELECTROCHEMISTRY
(2022)
Article
Chemistry, Organic
Zhong-Wei Hou, Zhong-Yi Mao, Hai-Chao Xu
Summary: In this study, tris(4-(tert-butyl)phenyl)amine was unexpectedly found to decompose into a tetraarylhydrazine during electrolysis, which can be used as an electrocatalyst for the synthesis of N-heteroaromatic compounds without the need for external chemical oxidants. This metal-free electrocatalytic method provides a straightforward access to N-heteroaromatic compounds from readily available materials.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
