Article
Chemistry, Physical
Adrian Tlahuext-Aca, Sarah Yunmi Lee, Shu Sakamoto, John F. Hartwig
Summary: A new method for the direct catalytic arylation of simple arenes using aryl bromides is described. The method does not rely on directing groups and instead utilizes a synergistic catalytic cycle involving phosphine-ligated silver complexes and palladium catalysts. Mechanistic experiments indicate that cleavage of the C-H bond by silver is the rate-determining step in the catalytic cycle.
Article
Chemistry, Multidisciplinary
Kristina Plevova, Peter Kisszekelyi, Denisa Vargova, Samuel Andrejcak, Viktor Toth, LukaS Fertal, Erik Rakovsky, Juraj Filo, Radovan Sebesta
Summary: This study demonstrates the diastereoselective double C-H heteroarylation of chiral ferrocenes using Pd-complexes with chiral mono-protected amino acids, resulting in a variety of functionalized compounds. The absolute configurations of CH-activation products were confirmed using X-ray crystallographic analysis and CD spectroscopy, while insights into the reaction mechanism and stereoinduction were provided by F-19 NMR kinetic study and DFT calculations.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Mingjie Liu, Junnan Liu, Jing Li, Zhenghua Zhao, Kai Zhou, Yueming Li, Peipei He, Jiashu Wu, Zongbi Bao, Qiwei Yang, Yiwen Yang, Qilong Ren, Zhiguo Zhang
Summary: This study demonstrates a novel strategy to address the limitations of aryl-ketone photocatalysts in terms of photostability and photoinduced electron transfer applications. By incorporating symmetric aryl ketones into conjugated covalent organic frameworks, improvements in photostability, electronic transfer efficiency, and structure-performance relationships were observed. This system provides a robust rule of thumb for designing new-generation aryl-ketone photocatalysts.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Andrea Aloia, Michele Casiello, Lucia D'Accolti, Caterina Fusco, Angelo Nacci, Antonio Monopoli
Summary: A novel Pd-catalysed oxidative coupling reaction between benzoic acids and vinylarenes or acrylates to form isocoumarins and phthalides is described. The reaction takes place smoothly in molten tetrabutylammonium acetate via selective C-H bond activation, employing a low amount of ligand-free palladium acetate as the catalyst, under atmospheric pressure of oxygen. Sub-stoichiometric copper acetate is also required as a reoxidant for palladium.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Rui Liu, Meng-Lan Shen, Lian-Feng Fan, Xiao-Le Zhou, Pu-Sheng Wang, Liu-Zhu Gong
Summary: Allylamines are important for synthesizing bioactive compounds and can be obtained through the palladium-catalyzed allylic C-H amination of 1,4-dienes. This reaction favors the formation of thermodynamically unstable Z-allylamines with aromatic amines. Aliphatic cyclic amines can also participate, but linear dienyl allylic amines are the main products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Nahiane Pipaon Fernandez, Gregory Gaube, Kyla J. Woelk, Mathias Burns, Damian P. Hruszkewycz, David C. Leitch
Summary: We present a new method for direct C-C bond formation using tandem C-O/C-H activation mediated by palladium catalyst. This approach allows for base-free direct C-H alkenylation by combining C-O oxidative addition at enol pivalates and concerted metalation-deprotonation of functionalized heterocycles. Mechanistic studies show that C-O oxidative addition is reversible and C-H activation occurs directly from the Pd(II) C-O oxidative addition product. In situ P-31 NMR spectroscopy reveals that (Cy3P)(2)Pd-(alkenyl)(OPiv) species is the predominant catalyst resting state during the reactions.
Article
Chemistry, Multidisciplinary
Jun Wu, Nikolaos Kaplaneris, Julia Poehlmann, Takuya Michiyuki, Binbin Yuan, Lutz Ackermann
Summary: The prevalence of C-aryl glycosides in biologically active natural products and approved drugs has motivated the development of efficient synthesis strategies. Palladium catalysts with prefunctionalized substrates have been commonly used, while ruthenium-catalyzed C-aryl glycoside synthesis has been challenging. In this study, a versatile ruthenium(II)-catalyzed meta-C-H glycosylation method was disclosed, allowing for the synthesis of meta-C-aryl glycosides from readily available glycosyl halide donors. The ruthenium catalysis exhibited mild reaction conditions, exceptional levels of anomeric selectivity, and exclusive meta-site-selectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Nihad Salameh, Federica Valentini, Olivier Baudoin, Luigi Vaccaro
Summary: We report a general and efficient enantioselective C-H arylation of aryl bromides using BozPhos as the bisphosphine ligand and SP-NHC-PdII as recoverable heterogeneous catalyst. By exploiting the release and catch mechanism of action, high enantioselectivities were achieved across different substrates containing methyl, cyclopropyl and aryl C-H bonds. The developed catalytic system provides a more sustainable solution for the synthesis of high added-value chiral products through recycling of the precious metal.
Article
Chemistry, Physical
Igor Beckers, Besir Krasniqi, Prashant Kumar, Daniel Escudero, Dirk De Vos
Summary: Two indoles linked by a C-C bond have emerged as promising scaffolds in medicinal chemistry. In this study, selective C-H/C-H cross-coupling of N-substituted indoles without directing groups was achieved under mild conditions, driven by molecular oxygen. The ligand-controlled selectivity can be exploited to achieve selective cross-coupling between two indoles with different substitution patterns.
Article
Chemistry, Organic
Jinping Lan, Weijie Yu, Ke You, Mengyu Xu, Bin Zhang, Yuanquan Wang, Tao Wang, Jin Luo
Summary: A facile and efficient method for dehalogenative arylation of unactivated alkyl halides using electrochemical reductive coupling has been developed. This method allows the synthesis of C(sp(2))-C(sp(3)) products in moderate to good yields. It does not require transition metal catalysts or redox mediators, and exhibits mild reaction conditions, broad substrate scope, and high tolerance towards functional groups. It is also applicable for gram-scale synthesis and late-stage functionalization of natural products.
Article
Chemistry, Multidisciplinary
Francesco Ferlin, Ioannis Anastasiou, Nihad Salameh, Takeru Miyakoshi, Olivier Baudoin, Luigi Vaccaro
Summary: A heterogeneous catalyst has been prepared for the intramolecular activation/cyclization reaction to synthesize indolines. The catalyst showed high efficiency through a release and catch mechanism, facilitated by iodide ligands. The heterogeneous nature of the catalyst was further utilized in the design of a continuous-flow protocol, enabling efficient recovery and reuse.
Article
Chemistry, Multidisciplinary
David Savary, Olivier Baudoin
Summary: C-H activation-based ring-forming methods are powerful for constructing complex molecular structures, especially useful for synthesizing chiral polycyclic aromatic hydrocarbons and other important organic electronic materials. A new enantioselective synthesis method using Pd-catalyzed C(sp(2))-H arylation protocol has been described, delivering diverse polycyclic compounds with high yield and good to excellent enantioselectivity, with investigation into their chiroptical properties.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Romain Melot, Marco Zuccarello, Diana Cavalli, Nadja Niggli, Michael Devereux, Thomas Burgi, Olivier Baudoin
Summary: This study showcases the unique reactivity profile of the IBiox ligand family in the Pd-0-catalyzed functionalization of nonactivated enantiotopic secondary C-H bonds, demonstrating high enantioselectivities for a broad range of valuable indane products. Analysis of the steric maps of the IBiox ligands provides insights into the correlation between enantioselectivity and spatial quadrants occupancy, offering a blueprint for designing more efficient ligands.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemistry & Molecular Biology
Meng-Yue Wang, Xue-Qing Zhu, Bao-Yin Zhao, Hong-Xia Zhang, Yong-Qiang Wang, Qiong Jia
Summary: In this study, the first palladium-catalyzed intramolecular C-H/C-H dehydrogenative coupling reaction of two simple arenes was reported to generate 5,6-dihydrophenanthridines. This approach has a wide substrate scope and good tolerance of functional groups, providing an efficient alternative synthesis route for important 5,6-dihydrophenanthridine compounds.
Article
Chemistry, Physical
Zhiqian Yu, Qianhui Liu, Yudong Yang, Jingsong You
Summary: This study demonstrates that phenolic compounds can serve as effective ligands to control the regioselectivity of ortho-C-H arylation reactions, enabling the synthesis of various biaryl phosphines in a streamlined and practical manner. The phosphine ligand library shows great potential in catalytic coupling reactions and exhibits unique chemoselectivity when compared with commercially available classic phosphine ligands.
Article
Chemistry, Physical
Amal Benzai, Fazia Derridj, Henri Doucet, Jean-Francois Soule
Summary: The study reports a Pd- or Ru-catalyzed arylation reaction that allows for the ortho-arylation of the aryl unit of 2-arylpyrazines with high regioselectivity and applicability to various substituted pyrazine compounds. Experimental results demonstrate that even pyrazines with 2,3-diphenyl substitution can yield the desired arylated product.
Article
Chemistry, Organic
Hai-Yun Huang, Haoran Li, Marie Cordier, Jean-Francois Soule, Henri Doucet
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Hai-Yun Huang, Amal Benzai, Xinzhe Shi, Henri Doucet
Summary: Researchers are focused on developing different procedures for direct functionalization of two different C-H bonds of the same organic molecule, which is currently an important research topic in organic chemistry. Over the past decade, the number of tools to control regiodivergent C-H bond functionalizations has significantly increased.
Article
Chemistry, Multidisciplinary
Xinzhe Shi, E. Daiann Sosa Carrizo, Marie Cordier, Julien Roger, Nadine Pirio, Jean-Cyrille Hierso, Paul Fleurat-Lessard, Jean-Francois Soule, Henri Doucet
Summary: Selective arylation at the beta-position of pyrazoles under ligand-free palladium catalysis with a simple base, without the need for an oxidant or further additives, is reported. The reaction proceeds smoothly with a variety of N-substituted pyrazoles using aryl bromides as the aryl source and a protic solvent. This beta-C-H bond arylation enables the construction of pi-extended poly(hetero)aromatic structures via further Pd-catalyzed combined alpha-C-H intermolecular and intramolecular C-H bond arylation, offering an atom-economical process.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Xinzhe Shi, Jian Zhang, Thierry Roisnel, Jean-Francois Soule, Henri Doucet
Summary: The reactivity of 2-benzyl-1,2,3-triazole in palladium-catalyzed direct arylation was investigated, leading to the selective synthesis of 2-benzyl-4-aryl-1,2,3-triazoles and subsequent synthesis of 4,5-diarylated 2-benzyl-1,2,3-triazoles. This selective 4,5-diarylation was successfully applied for the synthesis of pi-extended polycyclic heteroaromatic structures phenanthro[9,10-d][1,2,3]triazoles through Pd-catalyzed C4- and C5-intermolecular arylations followed by Pd-catalyzed C-H intramolecular arylation.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Haoran Li, Hai-Yun Huang, Thierry Roisnel, Henri Doucet
Summary: This method describes the regioselective palladium-catalyzed direct arylation of 6,7-difluorobenzo[d]imidazole using aryl bromides as coupling partners, with a preference for the C2-carbon of the difluorobenzo[d]imidazole. It tolerates a variety of substituents at different positions on the aryl bromide, as well as N-containing heteroaryl bromides.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Marie Peng, Jinqiang Lin, Wei Lu, Thierry Roisnel, Veronique Guerchais, Henri Doucet, Jean-Francois Soule
Summary: The utility of C-H bond functionalization of metalated ligands for the elaboration of aryl-functionalized difluorinated-1-arylisoquinolinyl Ir(III) complexes has been explored, resulting in the regioselective arylation of C-H bonds flanked by difluoroaryl units. Post-functionalization allows for the introduction of thermally sensitive functional groups, and all obtained complexes emit red phosphorescence with similar lifetimes.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Jian Zhang, Xinzhe Shi, Henri Doucet
Summary: This study explores a Pd-catalyzed annulative pi-extension reaction of 1-arylpyrroles using 1,2-dihalobenzenes as coupling partners, leading to the selective synthesis of pyrrolo[1,2-f]phenanthridines. The higher reactivity of the pyrrole C2-H bond allows for successful access to substituted pyrrolo[1,2-f]phenanthridines.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
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)
Article
Chemistry, Applied
Linhao Liu, Henri Doucet
Summary: The reactivity of 1,2-dihalobenzenes in palladium catalyzed polyheteroarylation via C-H bond functionalization was investigated. The first catalytic cycle using thiophene as the heteroarene gives the expected 2-(2-bromophenyl)thiophenes. In the course of the second catalytic cycle, in the presence of heteroarenes having a free C3-position, a partial Pd-1,4-migration occurred giving rise to aryl-substituted biheteroarenes such as 2 '-aryl-2,3 '-bithiophenes as well as the expected 1,2-di(thiophen-2-yl)benzenes. The best selectivities in favor of the formation of 2 '-aryl-2,3 '-bithiophenes were obtained with electron-rich 1,2-dihalobenzenes. A wide variety of thiophene derivatives bearing useful functions such as formyl, acetyl, cyclopropylmethanone, 2-methyl-1,3-dioxolane, ester, nitrile or chloro was tolerated allowing to prepare poly-functionalized 2 '-aryl-2,3 '-bithiophenes. Moreover, this one pot preparation of 2 '-aryl-2,3 '-bithiophenes employs a low loading of an air stable commercially available palladium source associated to an inexpensive base.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Linhao Liu, Henri Doucet
Summary: The reactivity of 1,2-dihalobenzenes in palladium-catalyzed C-H bond functionalization is difficult to control, while C3-substituted heteroarenes can be used to synthesize a variety of functionalized 1,2-heteroarylated benzene derivatives in high yields. Only a few heteroarenes with a free C3 position allow the preparation of 1,2-heteroarylated benzenes.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Organic
Manisha Durai, Linhao Liu, Pierre Frere, Thierry Roisnel, Veronique Guerchais, Henri Doucet
Summary: The reactivity of benzo[1,2-b: 4,5-']dithiophene-4,8-dione in Pd-catalyzed C-H arylation was studied. Selective mono-C2-arylated benzo[1,2-b: 4,5-b']dithiophene-4,8-diones were obtained using aryl bromides as aryl source and carbonate bases in 1,4-dioxane. These conditions were effective for coupling with various aryl bromides, including those with electron-rich and electron-poor substituents. Photophysical properties of arylated compounds were characterized through experimental and theoretical studies.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Marie Peng, Chang-Sheng Wang, Pan-Pan Chen, Thierry Roisnel, Henri Doucet, K. N. Houk, Jean-Francois Soule
Summary: We describe a Rh(III)-catalyzed ortho-C-H bond functionalization of nitroarenes with 1,2-diarylalkynes and carboxylic anhydrides. The reaction unexpectedly produces 3,3-disubstituted oxindoles with the formal reduction of the nitro group under redox-neutral conditions. This transformation allows the synthesis of oxindoles with a quaternary carbon stereocenter using nonsymmetrical 1,2-diarylalkynes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Marie Peng, Denis Ari, Thierry Roisnel, Henri Doucet, Jean-Francois Soule
Summary: We present a versatile Rh(i)-catalyzed cascade reaction that combines C(sp(2))-H bond functionalization and amidation between N-arylphosphanamines and acrylates. This innovative approach allows for the rapid synthesis of dihydroquinolinone scaffolds, which are commonly found in various pharmaceuticals. The involvement of a Rh-H intermediate and the substrate inhibition through catalyst saturation were revealed through detailed mechanistic investigations.
Article
Electrochemistry
A. Benzai, F. Derridj, O. Mouadili, M. Azzouzi, M. Kaddouri, K. Cherrak, R. Touzani, A. Aouniti, B. Hammouti, R. Elatki, H. Doucet
Summary: This study investigates the inhibition of mild steel corrosion in a molar hydrochloric acid medium by benzoxazol derivatives compounds. The research used gravimetric and electrochemical methods, considering factors such as inhibitor concentration, temperature, and duration of immersion. The results showed satisfactory coherence and theoretical calculations revealed a good correlation with the experimental results.
PORTUGALIAE ELECTROCHIMICA ACTA
(2021)
Article
Chemistry, Organic
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)
