Article
Chemistry, Organic
Guo-Shu Chen, Jia-Hui Li, Shu-Jie Chen, Wen-Xia Lin, Hai Ren, Dong-Sheng Deng, Yun-Lin Liu
Summary: This study reports a tartaric acid-catalyzed three-component reaction for the synthesis of meta-alkenylated aryl alkyl ethers in a single step. Initial mechanistic studies indicate that the free hydroxy group of p-quinol plays a crucial role in initiating the conjugate addition process. Additionally, meta-functionalized phenols can also be obtained in the absence of alcohols.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Mingming Huang, Man Tang, Jiefeng Hu, Stephen A. Westcott, Udo Radius, Todd B. Marder
Summary: A Cu-catalysed borylation reaction can achieve high-yield synthesis of arylboronic esters from aryl alkyl sulfones, while selective cleavage of cyclic sulfones can be achieved through Cu-mediated or Cu-free processes to prepare sulfonyl-containing boronate esters.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
John M. Halford-McGuff, Eva M. Israel, Matthew J. West, Julien C. Vantourout, Allan J. B. Watson
Summary: We have developed a method for the direct coupling of arylboronic acid N-methyliminodiacetic acid esters with amine and alcohol nucleophiles. This method allows for the synthesis of a wide range of C-N and C-O cross-coupled products, expanding the scope of organoboron components that can be used in this type of reaction.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Yunhui Feng, Hang Luo, Fangnian Yu, Qian Liao, Luqing Lin
Summary: Here, we present a visible-light-promoted single nickel catalysis for achieving various C-N couplings of aryl chlorides/bromides and diverse N-nucleophiles using sodium iodide as the activator. The single nickel catalyst plays a dual role in halogen exchange and C-N coupling, which are crucial for obtaining the desired coupling products. This catalytic process eliminates the need for an exogenous photocatalyst and offers a sustainable and efficient approach for mild C-N coupling. Experimental studies, along with UV-vis and NMR analyses, demonstrate that the halogen exchange between both Ni-II and Ni-III-halide complexes and the iodide anion is a significant process in the formation of coupling products.
Article
Chemistry, Multidisciplinary
Runqing Zhu, Qianqian Sun, Jing Li, Luohao Li, Qinghe Gao, Yakun Wang, Lizhen Fang
Summary: Selective hydroxylation of alkyl aryl ethers has been established using a ruthenium(ii) catalyst, hypervalent iodine(iii), and trifluoroacetic anhydride via a radical mechanism. This method is tolerant of a wide range of substrates and provides a facile and efficient way to synthesize clinical drugs on a gram scale.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Weiqi Liu, Xinghao Jin, Dawei Ma
Summary: The requirement of higher reaction temperatures for SNAr reaction between thiols and less reactive electron-poor aryl halides has led to the development of metal- and photo-catalyzed methods. In this study, the SNAr reaction between thiols and most electron-poor aryl halides was found to occur at RT-60°C using K2CO3 and DMAc. Additionally, two oxalic diamide ligands were identified to enable Cu-catalyzed coupling reactions with low catalytic loadings for unreactive (hetero)aryl halides, offering a promising approach for preparing (hetero)aryl thioethers.
Article
Chemistry, Multidisciplinary
Kenshiro Hitoshio, Hiroki Yamagishi, Jun Shimokawa, Hideki Yorimitsu
Summary: A diverse range of aryl chlorides underwent silylation using sodium silylsilanolate reagents in the presence of a Ni(cod)(2) catalyst complexed with phosphine ligands. The reaction conditions were mild and allowed for silylation of various aryl chlorides, including functionalised drug molecules.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Zhenlei Zou, Heyin Li, Mengjun Huang, Weigang Zhang, Sanjun Zhi, Yi Wang, Yi Pan
Summary: This work presents a general strategy for metal-catalyzed cross-coupling of fluoroalkyl radicals with aryl halides under electrochemical conditions. By using paired electrolysis, the contradiction between anodic oxidation of fluoroalkyl sulfinates and cathodic reduction of low-valent nickel catalysts can be effectively addressed, thus allowing for direct introduction of fluorinated functionalities into aromatic systems.
Article
Chemistry, Multidisciplinary
Qiaoli Li, Lanting Xu, Dawei Ma
Summary: Direct N-arylation of sulfonamides using a combination of copper and oxalamides (or 4-hydroxypicolinamides) as catalysts is an efficient method. It allows for a wide range of reactions between sulfonamides and (hetero)aryl bromides, and even works well with primary sulfonamides and (hetero)aryl chlorides under the catalysis of Cu2O and a 4-hydroxypicolinamide.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Aleria Garcia-Roca, Raul Perez-Soto, Georgiana Stoica, Jordi Benet-Buchholz, Feliu Maseras, Arjan W. Kleij
Summary: Metal-catalyzed propargylic transformations are a powerful tool in organic synthesis for forming new carbon-carbon and carbon-heteroatom bonds. However, there is limited knowledge about the mechanistic intricacies of asymmetric propargylic reactions with challenging heteroatom substitution, presenting an inspiring challenge. This study presents a detailed mechanistic analysis of a propargylic sulfonylation reaction promoted by a chiral Cu catalyst through experimental techniques and computational studies. Surprisingly, the enantio-discriminating step was found to be the proto-demetalation step, rather than the coupling between the nucleophile and the propargylic precursor.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Xinmiao Huang, Ling Tang, Zhiyong Song, Shuangshuang Jiang, Xianmao Liu, Ming Ma, Bo Chen, Yuanhong Ma
Summary: A nickel catalysis system has been developed for the desulfonylative C(sp(2))-C(sp(2)) reductive cross-coupling reactions of aryl sulfone derivatives with aryl bromides to form diverse biaryl compounds. The isolated and confirmed Ar-Ni(II)-SO(2)CF3 complex with a phosphine ligand through oxidative addition of aryl sulfone to Ni(0) species provides solid evidence for understanding the C(Ar)-SO2 bond activation and reaction mechanism.
Article
Chemistry, Organic
Peng Yang, Xia Wang, Liang Wang, Jiahua He, Qian Zhang, Dong Li
Summary: A novel metal-free C-N bond formation method was developed through oxidative cross-dehydrogenative coupling between iodoarenes and acylanilides, mediated by mCPBA. The reaction exhibited high para-selectivity with retention of the iodine atom, enabling further transformations. This method is characterized by substrate availability, easy operation, and atom economy, providing a simple and efficient route for the preparation of functionalized N-aryl amides.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Yunxia Liu, Xin Li, Qing Liu, Xinjin Li, Hui Liu
Summary: The electromagnetic mill (EMM) has enabled the palladium-catalyzed borylation of aryl bromides under solvent-free conditions with low palladium catalyst loading (0.05-0.5 mol %). This method offers numerous advantages, including a wide substrate scope, tolerance towards various functional groups, short reaction times, no additional heating requirements, and practical gram-scale synthesis. The EMM system not only shows promising potential for industrial applications, but also expands the possibilities of solvent-free solid-state metal-catalyzed syntheses.
Article
Chemistry, Organic
Mo Yu, Kaikai Niu, Ziwen Wang, Yuxiu Liu, Qingmin Wang
Summary: This study presents a protocol for visible-light-induced perfluoroalkylation reactions of aryl acrylic acids, which is important for late-stage modification of biologically active molecules. The reactions proceed in a decarboxylative manner using perfluoroalkyl iodides as radical precursors and inexpensive eosin Y as a photocatalyst. The easy accessibility of perfluoroalkyl iodides and the broad substrate scope, mild conditions, and metal-free catalyst make this protocol applicable for transforming inexpensive raw materials to high-value chemicals.
Article
Chemistry, Organic
Jing-Ao Ren, Jin-He Na, Chao Gui, Chengping Miao, Xue-Qiang Chu, Mengtao Ma, Hao Xu, Xiaocong Zhou, Zhi-Liang Shen
Summary: A nickel-catalyzed direct cross-coupling between unactivated aryl fluorides and aryl bromides was achieved. This one-pot reaction proceeds effectively at room temperature in THF, avoiding the use of preformed and sensitive organometallic reagents. The desired biaryls are produced in modest to good yields via C-F bond cleavage in the presence of a phosphine ligand and magnesium powder (with or without TMSCl).
