Article
Chemistry, Organic
Jin-He Na, Xiang Liu, Jia-Wen Jing, Jing Wang, Xue-Qiang Chu, Mengtao Ma, Hao Xu, Xiaocong Zhou, Zhi-Liang Shen
Summary: A step-economical and efficient one-pot reaction was developed for the direct cross-coupling of aryl fluorosulfate with aryl bromide. This reaction, conducted at room temperature in THF solvent, does not require the use of preprepared/commercial organometallic reagents. By utilizing nickel catalyst, magnesium turnings, and lithium chloride, the desired biaryls were obtained in moderate to good yields with reasonable functional group compatibility.
Article
Chemistry, Applied
Neil K. Adlington, Paul S. Siedlecki, Ian Derrick, Simon D. Yates, Andrew D. Campbell, Paula Tomlin, Thomas Langer
Summary: The plant-scale manufacture of AZD5069 faced challenges in removing palladium residues and dealing with the increasing costs of metal, ligand, and scavenger. An alternative copper-catalyzed reaction was developed and successfully operated.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2022)
Article
Chemistry, Applied
Jing-Ao Ren, Xue Chen, Chao Gui, Chengping Miao, Xue-Qiang Chu, Hao Xu, Xiaocong Zhou, Mengtao Ma, Zhi-Liang Shen
Summary: A step-economical and operationally simple nickel-catalyzed cross-electrophile coupling reaction was developed, enabling the coupling of aryl phosphates and aryl bromides through C-O bond cleavage without the use of moisture-labile and uncommonly available organometallics. The reaction proceeded smoothly in the presence of magnesium turnings and lithium chloride in THF solvent, providing moderate to good yields of biaryls with reasonable functionality tolerance.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Physical
Regina M. Oechsner, J. Philipp Wagner, Ivana Fleischer
Summary: We present a catalytic system that allows for mild and fast coupling of aryl chlorides with primary, secondary, and previously challenging tertiary alkyl thiols using an air-stable nickel(II) precatayst in combination with cost-effective potassium acetate as a base at room temperature. This system exhibits excellent tolerance towards various functional groups and yields thioethers in high yields, including pharmaceutical compounds. The chemoselective functionalization of disubstituted substrates is successfully demonstrated.
Article
Chemistry, Multidisciplinary
Guangwu Sun, Herui Liu, Xiu Wang, Wenbo Zhang, Wenjun Miao, Qinyu Luo, Bing Gao, Jinbo Hu
Summary: In this manuscript, a novel palladium-catalyzed coupling reaction between gem-difluoroalkenes and aryl boronic acids is reported, which yields bioactive indane-type ketones with an all-carbon alpha-quaternary center. The mechanism involves a water-induced defluorination and cross-coupling cascade pathway, supported by characterization and stoichiometric reactions of the key intermediates RCF2PdII. The use of vinyl difluoromethylene motif as an in situ carbonyl precursor is unprecedented in transition-metal-catalyzed coupling reactions, and it is expected to spark broad interest in ketone synthesis, fluoroalkene functionalization, and design of new synthetic protocols based on the unique reactivity of difluoroalkyl palladium(II) species.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Bingxiang Xue, Jie Shen, Sourav Manna, Angelino Doppiu, Lukas J. Goossen
Summary: A new catalyst has been discovered that can selectively introduce a primary amino group into aromatic compounds, and it can efficiently promote the amination reaction to synthesize primary anilines within 30 minutes.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Sheng-Qi Qiu, Yu Chen, Xiang-Jun Peng, Shi-Jiang He, Jun Kee Cheng, Yong-Bin Wang, Shao-Hua Xiang, Jun Song, Peiyuan Yu, Junmin Zhang, Bin Tan
Summary: In this study, we achieved the arene-alkene Suzuki-Miyaura coupling reaction between hindered aryl halides and vinyl boronates by designing appropriate ligands and reaction parameters. The axially chiral acyclic aryl-alkenes obtained exhibited remarkable efficiency, enantioselectivity, and E/Z selectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Jyoti M. Honnanayakanavar, Jagadeesh Babu Nanubolu, Surisetti Suresh
Summary: This study presents a novel copper-catalyzed tandem reaction for the efficient synthesis of a specific three-ring compound, which has been successfully applied to the total synthesis of the anticancer drug TIC10/ONC201.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Binyang Jiang, Shi-Liang Shi
Summary: In this study, the first Pd-catalyzed aryl-alkyl cross-coupling of alkylzirconocenes and aryl halides was reported, with the critical role of a commercially available N-heterocyclic carbene (IPr) ligand for the palladium catalyst. This mild protocol tolerates various functional groups and heterocycles and is applicable to both terminal and internal alkenes.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Organic
Ying Chen, Sailuo Li, Lanting Xu, Dawei Ma
Summary: N-1-(2,6-Dimethylphenyl)-N-2-(pyridin-2-ylmethyl)-oxalamide (DMPPO) was found to be a more effective ligand for copper-catalyzed coupling reaction than previously reported ones. Only 3 mol % CuCl and DMPPO are needed for complete coupling at 100 degrees C (for bromides) and 80 degrees C (for iodides). Both (hetero)aryl and alkyl substituted 1-alkynes showed good reactivity, resulting in the formation of diverse internal alkynes.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Tianna Jing, Ning Liu, Caixia Xu, Qingqing Bu
Summary: The direct synthesis of diarylethynes from less-reactive aryl chlorides and calcium carbide was achieved by palladium catalysis. The coupling reaction showed a broad substrate scope and could be applied to highly sterically hindered reaction systems.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Daniel Sowa Prendes, Florian Papp, Nagesh Sankaran, Nardana Sivendran, Frederike Beyer, Christian Merten, Lukas J. Goossen
Summary: Arylglycines, which are important pharmacophores in several top-selling drugs, can now be synthesized from abundant aryl chlorides using a Pd-catalyzed Schollkopf-type amino acid synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Qiang Li, Maoshuai Zhu, Xufei Yan, Ying Xia, Xiangge Zhou
Summary: A palladium-catalyzed annulative reaction between aniline and propargyl alcohol has been developed, resulting in versatile indole skeletons with potential applications. The reaction utilizes propargyl alcohols as internal or terminal alkynes for the formation of 3-alkenylindoles or 3-alkynylindoles through C-H/C-C activation.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Geyang Song, Ding-Zhan Nong, Qi Li, Yonggang Yan, Gang Li, Juan Fan, Wei Zhang, Rui Cao, Chao Wang, Jianliang Xiao, Dong Xue
Summary: This study demonstrates an easy, efficient, and economic method for synthesizing anilines. By directly exciting light, the amination of aryl halides with ammonium salts can be catalyzed using a Ni(OAc)2-bipyridine complex, allowing a broad range of aryl chlorides and bromides to be converted into primary (hetero)arylamines without the need for an external photosensitizer. The photoinduced generation of Ni(I)-bipyridine species is believed to play a key role in this catalytic cycle.
Article
Chemistry, Organic
Giorgio Rizzo, Gianluigi Albano, Teresa Sibillano, Cinzia Giannini, Roberta Musio, Fiorenzo G. Omenetto, Gianluca M. Farinola
Summary: This paper reports the application of a silk fibroin-supported Palladium catalyst (Pd/SF) in Suzuki-Miyaura and Ullmann coupling reactions of aryl chlorides. The existence of catalytic pockets where monoatomic palladium species can form stable complexes with SF is hypothesized and supported by experimental analysis. The size of the catalytic pocket of Pd/SF is estimated to be approximately 15 angstroms using computational modeling.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
