Article
Chemistry, Multidisciplinary
Julia R. Dorsheimer, Melissa A. Ashley, Tomislav Rovis
Summary: This study reports a new method to activate alpha-3 degrees amines for deaminative arylation by condensing with an electron-rich aldehyde and combining this reactivity with nickel metallaphotoredox to generate benzylic quaternary centers. The reaction is accelerated by added ammonium salts, which inhibit nickel black formation and accelerate the overall reaction rate. The study demonstrates a broad scope of coupling partners and shows an expedited synthesis of ALK2 inhibitors.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
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
Wen-Xin Li, Bo-Wen Yang, Xuan Ying, Zhuo-Wen Zhang, Xue-Qiang Chu, Xiaocong Zhou, Mengtao Ma, Zhi-Liang Shen
Summary: The direct cross-coupling of diaryl sulfoxides with aryl bromides via C-S bond cleavage was achieved using nickel(II) as the catalyst, 1,2-bis(diphenylphosphino)ethane (dppe) as the ligand, and magnesium turnings as the reducing metal in THF. This reaction showed a wide range of substrates and could be used for gram-scale synthesis. The one-pot reaction is operationally simple and economically efficient.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Multidisciplinary Sciences
Lara E. Zetzsche, Jessica A. Yazarians, Suman Chakrabarty, Meagan E. Hinze, Lauren A. M. Murray, April L. Lukowski, Leo A. Joyce, Alison R. H. Narayan
Summary: This study demonstrates the use of cytochrome P450 enzymes for biocatalytic cross-coupling reactions, enabling the formation of sterically hindered biaryl bonds through oxidative C-C bond formation. By engineering the substrate and atroposelectivity of the P450 enzyme, a highly efficient and selective process has been developed.
Article
Chemistry, Inorganic & Nuclear
Pamela Podchorodecka, Blazej Dziuk, Roman Szostak, Michal Szostak, Elwira Bisz
Summary: N-heterocyclic carbenes (NHCs) have been developed as a major direction in ancillary ligand development for stabilizing reactive metal centers. This study presents a new class of sterically-hindered, wingtip-flexible NHC ligands with N,C-chelating oxazole donors, synthesized through modular arylation of oxazole derivatives. The ligands' structure, electronic properties, and coordination chemistry to Ag(i), Pd(ii), and Rh(i) are described, as well as their preliminary catalytic activity in coupling and hydrosilylation reactions. The findings highlight the potential of these NHC ligands in inorganic and organometallic chemistry.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Pamela Podchorodecka, Blazej Dziuk, Roman Szostak, Michal Szostak, Elwira Bisz
Summary: N-heterocyclic carbenes have attracted significant attention as ancillary ligands for stabilizing reactive metal centers. This study reports a new class of wingtip-flexible NHC ligands that feature sterically-hindered N,C-chelating oxazole donors. The synthesis, characterization, and evaluation of their properties and coordination chemistry to Ag(i), Pd(ii), and Rh(i) are described. The study also presents preliminary studies of their catalytic activity in coupling and hydrosilylation reactions. These NHC ligands are expected to have broad interest in inorganic and organometallic chemistry due to their potential for stabilizing reactive metals.
DALTON TRANSACTIONS
(2023)
Editorial Material
Chemistry, Multidisciplinary
Javier F. Reynes, Felipe Garcia
Summary: Several mechanochemically heated processes have been published, but precise control over mechanochemical catalysed coupling reactions has been difficult. A recent report demonstrates a programmable jar heater manifold that efficiently enables the Suzuki-Miyaura-type cross coupling reaction of aryl sulfamates and aryl boronic acid species. This methodology can be easily upscaled 200-fold using twin-screw extrusion methodologies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biochemical Research Methods
Qiuyu Lin, Luyun Xue, Jiannan Sun, Yuanchao Wang, Heyong Cheng
Summary: In this study, a TMSOK-assisted Suzuki-Miyaura coupling strategy was designed for the microsynthesis of biaryls in PSI, achieving rapid and high-yield reactions. Furthermore, a high-sensitivity and selective PSI-MS method was developed for quantitative analysis of aryl bromides and other brominated pollutants. This method requires minimal or no sample pretreatment in real samples.
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
(2022)
Article
Chemistry, Applied
Wenhua Lin, Liping Zhang, Yanping Ma, Tongling Liang, Wen-Hua Sun
Summary: The sterically hindered 2-iminopyridine derivatives and their palladium chlorides complexes efficiently catalyze the Suzuki-Miyaura coupling reaction in aqueous solution, with good substrate scope and reusability for multiple batches. The spontaneous separation of coupling products in the aqueous medium adds to the process's appeal, while the catalytic performance can be significantly influenced by UV irradiation due to the photoisomerization of the catalysts' azo units. Overall, these titled palladium complexes offer a green, sustainable, cost-effective, and convenient method for synthesizing SMC products at a multi-gram scale.
APPLIED ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Chau Ming So, On Ying Yuen, Shan Shan Ng, Zicong Chen
Summary: This study presents a general chemoselective Suzuki-Miyaura coupling using a Pd/L33 catalyst, showing efficient coupling of polyhalogenated aryl triflates by controlling reactivity order and key factors, achieving high yields and chemoselectivity with low Pd catalyst loading.
Article
Chemistry, Applied
Sara Payamifar, Foad Kazemi, Babak Kaboudin
Summary: This study introduced a convenient nickel-catalyzed protocol for the Suzuki-Miyaura coupling reaction using a simple mixture of Ni(II) and unfunctionalized beta-cyclodextrin in water. The environmentally friendly and cost-efficient method allows the synthesis of biaryls from arylboronic acids and various aryl halides. The catalyst can be recycled for multiple runs with only a small decrease in catalytic activity.
APPLIED ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Qianqian Lu, Haixing Guan, Yan-En Wang, Dan Xiong, Tingzhi Lin, Fei Xue, Jianyou Mao
Summary: A visible-light-promoted nickel/photoredox-catalyzed reductive cross-coupling reaction between vinyl bromides and benzyl chlorides has been reported, enabling the synthesis of a diverse array of enantioenriched allylic centers in good yields and high enantioselectivities.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Kenji Ota, Kazunori Nagao, Hirohisa Ohmiya
Summary: This method synthesizes sterically hindered alpha-hydroxy carbonyl compounds through radical-radical coupling. It allows for the use of primary, secondary, and tertiary aliphatic carboxylic acids to introduce various alkyl substituents onto ketone moieties of alpha-ketocarbonyls under mild reaction conditions.
Article
Biochemistry & Molecular Biology
Wansheng Huang, Shengtang Huang, Zhoutong Sun, Wuyuan Zhang, Zhigang Zeng, Bo Yuan
Summary: In this study, an effective chemoenzymatic halogenation method was developed to transform freely rotating biaryl bonds to sterically hindered axis. The yields of the tribrominated biaryl products were high, and a one-pot, two-step chemoenzymatic strategy was proposed for the synthesis of sterically hindered biaryls.
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)
