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
Zijian Li, Wenxuan Sun, Xianxu Wang, Luyang Li, Yong Zhang, Chao Li
Summary: This method utilizes alcohols and aryl bromides as coupling partners, combining anodic preparation and nickel catalysis to efficiently construct C(sp(2))-C(sp(3)) bonds. The nickel-catalyzed paired electrolysis reaction showcases a broad substrate scope suitable for the synthesis of multifunctional compounds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(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, Organic
Yi-Ming Wei, Xiao-Di Ma, Meng-Fei Wang, Xin-Fang Duan
Summary: Fe-catalyzed difunctionalization of aryl titanates through double C-H activation has been developed. Aryl titanates are arylated via ortho C-H activation, followed by ipso electrophilic trapping of the C-Ti bond. The ortho C-H arylation is promoted by a 1,2-Fe/Ti heterobimetallic arylene intermediate and involves another ortho C-H activation directed by benzamides, esters, and nitriles.
Article
Chemistry, Multidisciplinary
Yunjung Baek, Theodore A. Betley
Summary: The reactivity of (L-Tr)Co towards various aryl azides was investigated to understand the electronic structure and reactivity of dipyrrinato cobalt aryl nitrenoid complexes. The synthesis of a Co-II diketimide complex and its reversible C-C bond cleavage to yield a monomeric Co nitrenoid complex was demonstrated. The study revealed the pre-equilibrium between [(L-Tr)Co(NC6F5)](2) and (L-Tr)Co(NC6F5), as well as the reductive coupling, fluoride expulsion, and N-group transfer reactivity of (L-Tr)Co(NC6F5).
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Daigo Hayashi, Tomohiro Tsuda, Ryo Shintani
Summary: A palladium-catalyzed skeletal rearrangement has been developed to synthesize highly fused tetrahydrophenanthrosilole derivatives via bond exchange. The reaction conditions can be tuned to produce different products, fused dihydrodibenzosilepin derivatives.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Bo-Sheng Zhang, Ying-Hui Yang, Fan Wang, Xue-Ya Gou, Xi-Cun Wang, Yong-Min Liang, Yuke Li, Zheng-Jun Quan
Summary: This paper presents the first case of a reductive coupling reaction using indene as a reducing agent, showing a broad substrate scope and various types of reactions. The formation of an eta(3)-palladium indene intermediate was confirmed through control experiments and density functional theory calculations, while the formation of palladium anion intermediates was excluded.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Physical
Mengwei Li, Junjun Shan, Georgios Giannakakis, Mengyao Ouyang, Sufeng Cao, Sungsik Lee, Lawrence F. Allard, Maria Flytzani-Stephanopoulos
Summary: In this work, a one-step conversion of methane to methanol using molecular oxygen as the oxidant in aqueous solutions with the presence of CO on copper or palladium-promoted Ir-ZSM-5 catalyst is reported. The addition of a second metal to Ir-ZSM-5 enhances catalyst activity and tunes product selectivity. The trimetallic system IrCuPd shows the best performance for methanol formation with good stability in cyclic operation.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2021)
Article
Chemistry, Organic
Zhijun Zuo, Armido Studer
Summary: In this study, a photoredox-catalyzed 1,3-oxyalkynylation reaction of cyclopropanes with EBXs was described, offering a wide substrate scope.
Article
Multidisciplinary Sciences
Dingyi Wang, Mingjie Li, Chengdong Shuang, Yong Liang, Yue Zhao, Minyan Wang, Zhuangzhi Shi
Summary: The authors report a method that appends arenes to arylphosphines via rhodium-catalyzed P(III)-directed ortho C-H activation, enabling one-fold, two-fold, and three-fold direct arylation of these compounds. This method provides a solution to the challenges associated with the modular preparation of biaryl monophosphines.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Applied
Hidemasa Hikawa, Taku Nakayama, Makiko Takahashi, Shoko Kikkawa, Isao Azumaya
Summary: This study demonstrates the direct use of benzylic alcohols in a multicomponent reaction with readily available isatoic anhydrides and amines in water to construct a series of 2-aryl quinazolinones. The one-pot synthetic method involves dehydrative N-benzylation of in situ generated anthranilamides, followed by an amide-directed benzylic C-H amination process. Independent rate measurements showed a kinetic isotope effect of 3.5, indicating that the benzylic C-H bond is cleaved in the rate-determining step. A gram-scale reaction was successfully carried out in 85% yield with simplified product isolation.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Paige E. Piszel, Brandon J. Orzolek, Alyssa K. Olszewski, Madeline E. Rotella, Amanda M. Spiewak, Marisa C. Kozlowski, Daniel J. Weix
Summary: Protonation of C-M bonds and metalation of C-H bonds are important steps in metal-catalyzed processes. The rate of protodemetalation (PDM) of arylnickel(II) complexes with various acids was studied, and evidence for a concerted, cyclic transition state for the PDM of C-Ni bonds was obtained. It was found that five-, six-, and seven-membered transition states are particularly favorable. The data also showed that the rate of protodemetalation is not always correlated with acidity, and certain acids can protodemetalate faster than predicted by pKa. The study revealed new avenues for C-H activation and strategies to control protodemetalation in nickel catalysis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Applied
Shuo He, Yujie Chen, Zhi-Bin Huang, Bao Li, Da-Qing Shi, Yingsheng Zhao
Summary: A palladium-catalyzed cross-coupling reaction between the ortho-C(sp(2)) atom of aromatic amines and aliphatic aziridines has been developed, enabling the construction of the O-aminophenethylamine skeleton via C-H activation. The reaction shows good substrate scope and can generate the O-aminophenethylamine skeleton in drugs or bioactive compounds in a one-step process.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Yong Zhang, Ya-Kui Sun, Ya-Ping Chang, Hui Shao, Yu-Ming Zhao
Summary: The rapid construction of molecules with all-substituted quaternary stereocenters is a significant but challenging task in organic synthesis. This study reports a novel palladium-catalyzed cascade reaction between alkene-tethered aryl iodides and carbon monoxide, providing a practical and powerful method for synthesizing complex polycyclic molecules containing aryl-substituted quaternary stereocenters. Mechanistic studies suggest that the reaction proceeds through a Heck-type carbonylative cyclization followed by a ketene-involved Friedel-Crafts acylation.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Jing Wang, Hui Wang, Zihan Wang, Linqiang Li, Cheng Qin, Xinjun Luan
Summary: This paper reports a highly chemoselective and regioselective vicinal trifunctionalization of aryl iodides using palladium/norbornene catalysis, introducing two distinct nitrogen and carbon electrophiles. The resulting products exhibit strong fluorescence emissions with full-color tunability, and product 7r can serve as a fluorescent probe specifically targeting lysosomes in living cells.
CHINESE JOURNAL OF CHEMISTRY
(2021)
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
Biochemistry & Molecular Biology
Cleve D. Mboyi, Ons Amamou, Paul Fleurat-Lessard, Julien Roger, Helene Cattey, Charles H. Devillers, Michel Meyer, Taoufik Boubaker, Jean-Cyrille Hierso
Summary: The carbon-carbon cross-coupling reaction of phenyl s-tetrazine units resulted in the formation of constrained bis(tetrazines) with original tweezer structures. The resulting compounds can serve as weak coordinating ligands with cationic silver, generating a series of bis(tetrazine)-silver(I) coordination complexes capable of tolerating a variety of counter anions. These complexes exhibit good coordination properties in both solid state and solution, forming polymeric chains in the former and showing stoichiometry and stability in the latter.
Article
Chemistry, Inorganic & Nuclear
Petr Vosahlo, Lea Radal, Marine Labonde, Ivana Cisarova, Julien Roger, Nadine Pirio, Jean-Cyrille Hierso, Petr Stepnicka
Summary: Anionic phosphinoferrocene amidosulfonates with sterically demanding tert-butyl groups were synthesized and used as ligands for zwitterionic (eta3-allyl)palladium(II) complexes. The preference for coordination of amide or sulfonate oxygen atoms was explained by electrostatic and solvation effects, and these complexes were applied as precatalysts for C-H arylation reactions with aryl iodides, showing good catalytic performance with a low loading of catalyst.
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
Julien Roger, Charline Sire, Anthonia Tsivery, Helene Cattey, Jean-Cyrille Hierso
Summary: We report a simple and efficient method for the peri-C-H functionalization of polyarylphosphines using aryl triflates as electrophile coupling partners. A [Rh(III)Cl2Cp*]2 precatalyst is employed to achieve high yields of polyarylated phosphines. This method is tolerant of various substituents and bulky polyaromatic triflate substrates.
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)
Review
Chemistry, Inorganic & Nuclear
Siva Sankar Murthy Bandaru, Jagrut Shah, Shatrughn Bhilare, Carola Schulzke, Anant R. Kapdi, Julien Roger, Jean-Cyrille Hierso
Summary: This review focuses on the applications of different ferrocenylphosphine ligands in transition metal-catalyzed cross-coupling strategies, including the asymmetric synthesis using chiral ferrocenyl phosphines. It also discusses the latest advances in the chemistry of symmetric achiral di- and polyphosphine ferrocene-based ligands related to metal-catalyzed bond-forming reactions. A cumulative table compiling significant work in this field is provided.
COORDINATION CHEMISTRY REVIEWS
(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
Chemistry, Multidisciplinary
Ahmad Daher, Oumaima Abidi, Jean-Cyrille Hierso, Julien Roger
Summary: A general palladium-catalysed selective C-H halogenation reaction was developed, allowing clean halogenation reactions on a variety of functionalized aromatic rings. This method utilizes simple alkali halides as the nucleophilic reagent and can be accomplished in a short time with microwave irradiation assistance. The reaction was successfully extended to substrates with diverse N-directing groups, including challenging s-tetrazine.
Article
Chemistry, Multidisciplinary
Houssein O. Nasrallah, Yuanyuan Min, Emmanuel Lerayer, Tuan-Anh Nguyen, Didier Poinsot, Julien Roger, Stephane Brandes, Olivier Heintz, Pierre Roblin, Franck Jolibois, Romuald Poteau, Yannick Coppel, Myrtil L. Kahn, Iann C. Gerber, M. Rosa Axet, Philippe Serp, Jean-Cyrille Hierso
Summary: Ultrasmall gold nanoparticles stabilized in networks by polymantane ligands were successfully utilized as highly selective heterogeneous gold precatalysts, providing control over selectivity and enabling a one-pot cascade reaction approach. The ability to assemble nanoparticles with controllable sizes and shapes within networks holds significant implications for various applications, while the synthesis of sub-2-nm gold NPs in dense networks using ditopic polymantanethiols was achieved.
