Article
Chemistry, Multidisciplinary
Shentong Xie, Yuqing Yin, Ya Wang, Jiannan Wang, Xiaoqian He, Ruopeng Bai, Renyi Shi
Summary: The electroreductive cross-electrophile coupling is a powerful, green, and efficient method for constructing challenging C-C bonds, which has attracted increasing attention from organic chemists. Most of the previous works focus on direct two-electrophile cross-coupling. In this work, a nickel-catalyzed three-electrophile electroreductive cross-electrophile coupling has been developed, offering a direct and convergent synthesis to target molecules from easily available and cheap substrates under mild conditions.
Article
Chemistry, Organic
Ya-Qiong Qi, Shuai Liu, Yan Xu, Yang Li, Tong Su, Hai-Liang Ni, Yuanji Gao, Wenhao Yu, Peng Cao, Ping Hu, Ke-Qing Zhao, Bi-Qin Wang, Bin Chen
Summary: We report an efficient Ni-catalyzed three-component cross-electrophile coupling reaction, which accomplishes dicarbofunctionalization of 1,3-dienes by forming two new C-C bonds in one reaction.
Review
Chemistry, Multidisciplinary
Takanori Iwasaki, Nobuaki Kambe
Summary: Carbon-fluorine bonds are stable but can be selectively transformed under appropriate conditions, making them useful synthetic methods in organic chemistry. This review focuses on C-C bond formation at monofluorinated sp(3)-hybridized carbons via C-F bond cleavage, including cross-coupling and multi-component coupling reactions. The mechanisms of C-F bond cleavage on sp(3)-hybridized carbon centers are categorized into three types: Lewis acids promoted F atom elimination, nucleophilic substitution with metal or carbon nucleophiles, and cleavage of C-F bonds via single electron transfer. Furthermore, the unique characteristics of alkyl fluorides compared to other (pseudo)halides as electrophilic coupling counterparts are discussed.
Review
Chemistry, Multidisciplinary
Yaowen Liu, Pengfei Li, Yanwei Wang, Youai Qiu
Summary: Electrochemistry employs electrons as an efficient and sustainable alternative to chemical oxidants or reductants, and has gained popularity for selective organic synthesis. The combination of electrochemistry with readily available electrophiles has emerged as a viable method for constructing challenging C-C and C-heteroatom bonds. This mini-review provides a systematic summary of the recent advances in electroreductive cross-electrophile coupling (eXEC) reactions, focusing on aryl and alkyl organic (pseudo)halides, as well as small molecules such as CO2, SO2, and D2O.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Ya-Ting Wen, Xiang-Tao Kong, Hong-Chao Liu, Cui-Tian Wang, Wan-Xu Wei, Bin Wang, Xue-Yuan Liu, Yong-Min Liang
Summary: An innovative 1,5-HAT cascade strategy has been proposed for nickel-catalyzed distal arylation via cross-electrophile coupling. It selectively activates the remote C(sp(3))-H bond through specific migration and uses Ar-I as the available electrophile for constructing the C(sp(3))-C(sp(2)) bond. The method shows broad applicability for benzylic and aliphatic N-fluorocarboxamides with yields up to 80%. Control experiments suggest that this reaction may be initiated by a radical process.
Article
Multidisciplinary Sciences
Wen Zhang, Lingxiang Lu, Wendy Zhang, Yi Wang, Skyler D. Ware, Jose Mondragon, Jonas Rein, Neil Strotman, Dan Lehnherr, Kimberly A. See, Song Lin
Summary: Recent research in medicinal chemistry has found a correlation between an increase in sp(3) carbons in drug candidates and their improved success rate in clinical trials. This study focuses on the development of robust and selective methods for constructing carbon(sp(3))-carbon(sp(3)) bonds. By using electrochemistry, the researchers achieve the selective activation of alkyl halides based on their electronic and steric properties, allowing for high selectivity in carbon(sp(3))-carbon(sp(3)) cross-electrophile coupling. This new protocol shows improved chemoselectivity and does not require a transition metal catalyst.
Article
Chemistry, Organic
Andrew C. Jones, William I. Nicholson, Jamie A. Leitch, Duncan L. Browne
Summary: The nickel-catalyzed cross-electrophile coupling of aryl halides and alkyl halides enabled by ball-milling is efficient and green, achieving reductive C-C bond formation under a mechanochemical manifold. The mechanical action provided by ball milling allows for the use of a variety of zinc sources to turnover the nickel catalytic cycle, resulting in the synthesis of 28 cross-electrophile coupled products.
Article
Chemistry, Physical
Bijan Mirabi, Austin D. Marchese, Mark Lautens
Summary: In this study, a nickel-catalyzed cross-electrophile coupling reaction of aryl chlorides and heteroaryl chlorides was reported, enabled by a synergistic combination of halide effects and the addition of a magnesium salt. Electronic-deficient aryl chlorides were found to perform the best in the reaction, and preliminary mechanistic evidence showed that MgCl2 is crucial for accelerating the reduction of Ni(II) while small quantities of iodide lead to improved yields.
Article
Chemistry, Multidisciplinary
Linlin Ding, Yue Zhao, Hongjian Lu, Zhuangzhi Shi, Minyan Wang
Summary: For the first time, a catalytic enantioselective propargyl-aryl cross-coupling between two electrophiles was achieved in a stereoconvergent manner. The potential utility of this conversion is demonstrated in the facile construction of stereoenriched bioactive molecule derivatives and medicinal compounds based on the diversity of acetylenic chemistry. Detailed experimental studies have revealed the key mechanistic features of this transformation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Tingzhi Lin, Yan-En Wang, Ning Cui, Miaohui Li, Rui Wang, Jiahui Bai, YiRan Fan, Dan Xiong, Fei Xue, Patrick J. Walsh, Jianyou Mao
Summary: A nickel-catalyzed cross-electrophile coupling reaction has been developed to generate a diverse array of ortho-arylated benzamide derivatives. The reaction shows good functional group tolerance and scalability.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Tingzhi Lin, Yan-En Wang, Ning Cui, Miaohui Li, Rui Wang, Jiahui Bai, YiRan Fan, Dan Xiong, Fei Xue, Patrick J. Walsh, Jianyou Mao
Summary: A nickel-catalyzed cross-electrophile coupling reaction between 1,2,3-benzotriazin-4(3H)-ones and aryl bromides has been developed, leading to a diverse array of ortho-arylated benzamide derivatives. The reaction exhibits good functional group tolerance and utilizes the ring opening of benzotriazinones followed by denitrogenation to obtain various benzamide derivatives (29 examples, 42-93% yield). The scalability of this transformation has been demonstrated.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Kartic Manna, Ranjan Jana
Summary: We describe a mild and highly selective palladium-catalyzed cross-electrophile coupling between aromatic diazonium salts and aryl iodides or diaryliodonium salts in a water-ethanol (2:1) medium. Mechanistic studies revealed the importance of ethanol in generating an active Pd(0) catalyst, and the counterion of the diazonium salt promotes the formation of a cationic Pd(II) species that facilitates subsequent oxidative addition to aryl iodides/diaryliodonium salts. The presence of silver(I) salt is crucial for maintaining the catalytic activity of palladium by removing iodide ions as precipitates.
Article
Multidisciplinary Sciences
Haigen Fu, Jingzhe Cao, Tianzhang Qiao, Yuyin Qi, Simon J. Charnock, Samuel Garfinkle, Todd K. Hyster
Summary: This study reports a highly chemoselective and enantioselective Csp(3)-Csp(3) XEC reaction catalyzed by flavin-dependent 'ene'-reductases (EREDs). The photoexcitation of the enzyme-templated charge-transfer complex enables the chemoselective reduction of alkyl halides and high enantioselectivity.
Article
Multidisciplinary Sciences
Kaluvu Balaraman, Christian Wolf
Summary: This study demonstrates the chemodivergent activation of monofluoroalkyl compounds towards either nucleophilic or electrophilic intermediates, expanding the scope of organofluorine chemistry and creating new synthetic opportunities for carbon-carbon and carbon-heteroatom bond formations.
Article
Chemistry, Physical
Jordan L. S. Zackasee, Samir Al Zubaydi, Blaise L. Truesdell, Christo S. Sevov
Summary: Mediator-assisted electrocatalysis is a general strategy to enhance the electroreductive cross-electrophile coupling (eXEC) reactions. Addition of a redox-matched mediator enables the catalyst-mediator systems to generate products in near-quantitative yield. This study also identifies a library of catalyst-mediator systems that can couple a wide range of substrate classes in high yields.
Article
Chemistry, Organic
Fuying Zhu, Yamei Lin
Summary: In this study, a low-metal iron-supported catalyst (Fe20/NC-Mg) was reported for the efficient synthesis of quinoxaline compounds, using water as a solvent and without additional bases. The synergistic effect of FeNx site and Mg (OH)2 nanorods in the catalyst played a key role in achieving high yields (82-91%) in 16 examples. The gram-level synthesis and reusability of the catalysts after four cycles demonstrated its industrial application potential.
Article
Chemistry, Organic
Mikhail Kozlov, Alexey Tyurin, Andrey Dmitrenok, Vyacheslav Rusak, Aleksander Fedorov, Igor Zavarzin, Yulia Volkova
Summary: This study presents a novel and practical synthesis method for phosphorus-substituted 1,3,4-thiadiazolines using phosphorylthioformic acid hydrazides and ketones. The protocol demonstrates operational simplicity, availability of reagents, and tolerance towards different functional groups.
Article
Chemistry, Organic
Jisna Jose, Thomas Mathew
Summary: 2-Cyclopentenone and its derivatives are highly esteemed synthetic intermediates with exceptional utility in organic synthesis. They are favored structural motifs in numerous pharmaceutical drugs and natural products, highlighting their significance. The review discusses the various methods used to synthesize cyclopentenones from 2016 to 2023.