Article
Chemistry, Multidisciplinary
Jun-Jie Tian, Wei Sun, Rui-Rui Li, Gui-Xiu Tian, Xiao-Chen Wang
Summary: A borane/gold(I) co-catalytic system was designed and applied in C-H functionalization reactions and cycloaddition reactions between tertiary amines and alpha-alkynylenones, efficiently introducing a furan ring into the amine molecule.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Roushan Prakash Singh, Soumen Sinhababu, Neal P. Mankad
Summary: This Perspective reviews recent advances and applications of Al/M heterobimetallic catalysis in various areas, including polymerization, epoxide activation and carbonylation. The mechanistic role of the aluminum site is highlighted, and a comprehensive perspective is constructed by including a broad range of Al-containing metalloligands and Al/M combinations.
Article
Chemistry, Physical
R. Tyler Mertens, Charles E. Greif, James T. Coogle, Gilles Berger, Sean Parkin, Mark D. Watson, Samuel G. Awuah
Summary: This study reports the development of a gold-catalyzed cross coupling reaction without oxidants, which can form biaryls without homocoupling of aryl halides. The study unveils the critical role of unsymmetrical tricoordinate Au(I) catalysts in this transformation.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Nurbey Gulia, Jaroslaw Fornalski, Adrianna Gumienna, Malgorzata Ambroziak, Slawomir Szafert
Summary: This study reports a method of palladium-catalyzed C-H arylation assisted with a 3,4,4-trimethylpyrazol-5-on directing group, which selectively provides mono- and di-ortho-arylated products. The steric hindrance between the directing group and the already introduced aryl substituent enables control of mono- vs. diarylation selectivity by the reaction temperature. A series of monosubstituted and disubstituted derivatives were obtained in good yields. In addition, a one-pot procedure for unsymmetrical double-arylation to give corresponding products was developed, and the synthesis and X-ray study of intermediate palladium metallacycles were conducted. The decarboxylative cleavage of the pyrazolone directing group under mild conditions gave synthetically useful hydrazones. Overall, this solution provides an alternative synthetic pathway for ortho arylated derivatives of arylhydrazines.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Baptiste Neil, Franck Lucien, Louis Fensterbank, Clement Chauvier
Summary: The study introduces a method for C(sp(2))-H bond silylation using an alternative silicon source that is readily accessible from commercially available precursors, without the need for expensive catalytic systems and noble metal catalysts, showing good generality.
Article
Chemistry, Multidisciplinary
Kai Liu, Tingrui Li, Duan-Yang Liu, Weipeng Li, Jian Han, Chengjian Zhu, Jin Xie
Summary: This study reports an unprecedented C-H bond functionalization of cyclopropenes enabled by dinuclear gold catalysis, resulting in highly selective C-H allylation, alkynylation, and halogenation reactions with organic halides. The reaction does not require strong external oxidants and affords access to functionalized cyclopropenes in moderate to good yields. The reductive elimination process for construct C-C or C-X bonds can be controlled by using different dinuclear gold catalysts.
SCIENCE CHINA-CHEMISTRY
(2021)
Article
Chemistry, Physical
Yuxi Wang, Bo Qiu, Lingfei Hu, Gang Lu, Tao Xu
Summary: The reverse concerted metalation-deprotonation (CMD) process is proposed as a key step in rationalizing a newly discovered Rh-catalyzed C-C/olefin-H cascade reaction, which features redox-neutral conditions with 100% atom economy, broad substrate scope, and high efficiency (23 examples, up to 85% yield). DFT calculations suggest that the reverse CMD process is crucial in kinetic override of the normal cut and sew process, leading to the activation of olefinic C-H bonds as the predominant pathway.
Article
Chemistry, Multidisciplinary
Alexander Purtsas, Marco Rosenkranz, Evgenia Dmitrieva, Olga Kataeva, Hans-Joachim Knoelker
Summary: In this paper, the oxygenation and amination reactions of tertiary arylamines are described. The key steps of these coupling reactions involve iron-catalyzed oxidative C-O or C-N bond formation, which typically provide the desired products in high yields and with excellent regioselectivity. These transformations are carried out using hexadecafluorophthalocyanine-iron(II) (FePcF16) as catalyst, with the presence of an acid or base additive, and only require ambient air as the oxidant.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Ryudai Michikita, Yoshinosuke Usuki, Tetsuya Satoh
Summary: A Rh(III)-catalyzed double C-H annulation of 3-(acetylamino)coumarins with internal arylacetylenes is reported, which selectively produces 8-aryl-6H- chromeno[4',3':4,5]pyrrolo[2,1-a]isoquinolin-6-ones accompanied by the formation of two C-C and two C-N bonds. This method also provides a straightforward route to natural product inspired pentacyclic pyrrolocoumarin derivatives from readily available building blocks.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Organic
Linhao Liu, Manisha Durai, Henri Doucet
Summary: The metal-catalyzed direct functionalization of two different C-H bonds of the same organic molecule, known as regiodivergent C-H bond functionalization, is an important research topic in organic chemistry. The number of tools to control such functionalizations has significantly increased over the last decades, with different metal sources being the most effective. Ru or Rh catalysts can be used for arylation of the aryl unit, while Pd or Cu catalysts can be used for arylation of the azole unit, allowing for regiodivergent direct arylation of aryl-substituted azoles.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Applied
Oleg Y. Lyakin, Dmitry S. Bushmin, Evgenii P. Talsi, Konstantin P. Bryliakov
Summary: This review summarizes the recent advances in homogeneous oxidation of hydrocarbon C(sp(3))-H bonds catalyzed by nickel and palladium complexes, and discusses the correlations between the catalyst structure, ligand properties, catalytic conditions, and catalytic reactivity (efficiency, chemoselectivity, and regioselectivity).
APPLIED ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Duan-Yang Liu, Jie Han, Kai Liu, Yaohang Cheng, Hairen Tan, Xiaoliang Yang, Weipeng Li, Jin Xie
Summary: This study presents a gold-catalyzed para-C-H arylation reaction at room temperature, successfully applied to monofluoroarenes. The method shows high para-selectivity and a broad substrate scope, providing a concise and efficient strategy for constructing structurally diverse para-arylated monofluoroarenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jyoti Dhankhar, Micha D. Hofer, Anthony Linden, Ilija Coric
Summary: This article presents a new selectivity mode for C-H arylation reactions, which is the preference for C(sp(2))-H activation next to alkyl groups. The study results indicate that this preference is related to the non-covalent interactions between the catalyst and the substrate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Huaxin Zhang, Yongge Xiong, Mu-Jia Luo, Ruchun Yang, Jiang Bai, Xian-Rong Song, Qiang Xiao
Summary: Here, a novel and sustainable electrochemically driven oxidative 5-exo-dig radical cyclization of N-propargylbenzamides with alcohols is described, providing a convenient method for the synthesis of structurally diverse oxazole ketals in moderate to good yields. This protocol is achieved under mild conditions in an undivided cell without the need for external transition-metal catalysts, chemical oxidants, and ketalization acids, and exhibits scalability, broad substrate scope, and excellent functional group compatibility. Mechanistic studies reveal that the reaction proceeds via a nucleophilic substitution process rather than ketalization.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Alexandra M. Zima, Oleg Y. Lyakin, Anna A. Bryliakova, Dmitrii E. Babushkin, Konstantin P. Bryliakov, Evgenii P. Talsi
Summary: Catalytic approaches to late-stage creation of new C-O bonds, especially via oxygenation of particular C-H groups in complex organic molecules, provide challenging tools for the synthesis of biologically active compounds and candidate drugs. The key role of the oxygen-transferring high-valent iron-oxygen species in selective oxygenation is now well established. In this Personal Account, recent data on the reactivity of bioinspired formally oxoiron(V) catalytically active sites toward organic substrates having C=C and C(sp(3))-H groups are analyzed, with a focus on the factors governing the oxidation chemo- and stereoselectivity.
