Article
Chemistry, Multidisciplinary
Fabio Bellina, Matteo Biagetti, Sara Guariento, Marco Lessi, Mattia Fausti, Paolo Ronchi, Elisabetta Rosadoni
Summary: A variety of 2-alkynyl(benzo)imidazoles have been synthesized by dehydrogenative alkynylation of (benzo)imidazoles with terminal alkyne in NMP under air in the presence of Ag2CO3 as the oxidant and Pd(OAc)(2) as the catalyst precursor. The data obtained in this study support a reaction mechanism involving a non-concerted metalation deprotonation (n-CMD) pathway.
Article
Chemistry, Multidisciplinary
Sheng Zhang, Junchao Yin, Ziyang Wang, Yang Li, Yukang Fu, Ji Ma, Zhilong Xie, Ming Bao
Summary: A palladium-catalysed aromative benzylic allylation and allenylation of benzyl chlorides with allyl and allenyl pinacolborates is reported for the first time. The reactions are conducted smoothly in the presence of a bidentate phosphine ligand, yielding good cross-coupling products. This new synthetic method exhibits excellent tolerance for various functional groups and is compatible with sensitive groups such as NO2, CF3, CN, and COOMe. The utilization of a bidentate ligand and heating is crucial for the transformation. DFT calculation results reveal the importance of wide-bite-angle bidentate ligands for the formation of an eta(1)-benzyl-eta(1)-allylpalladium intermediate and the thermodynamic favorability of the normal coupling reaction.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Roberta A. Kehoe, Mark E. Light, David J. Jones, Gerard P. McGlacken
Summary: One-pot processes offer an environmentally friendly and time-saving approach to building complex molecules. This study presents a phosphine-free, inorganic base free, multi-step, one-pot reaction sequence for the rapid synthesis of complex medicinally relevant heterocycles. The approach combines three distinct reactions using a single pre-catalyst and achieves excellent yields. The study also reports favorable mass productivity, environmental impact factor, solvent intensity, and process mass intensity values.
Article
Chemistry, Organic
Milos Petkovic, Milos Jovanovic, Predrag Jovanovic, Milena Simic, Gordana Tasic, Vladimir Savic
Summary: Pyrrole derivatives with C(2)-aryl substituents are an important and widespread class of heterocyclic compounds. A novel approach combining the dual role of arylating agent as nitrogen protecting group and involved in the arylation step has been developed for the direct arylation synthesis of C(2)-arylpyrroles. The deprotection as a final stage is carried out simultaneously utilizing amines as reacting components, leading to mild conditions and exclusive C(2) selectivity.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Organic
Hannah M. Holst, Jack T. Floreancig, Casey B. Ritts, Nicholas J. Race
Summary: This study demonstrates the synthesis of beta-phenethylamine products through the treatment of unsymmetrical 2,3-disubstituted aziridines with TiCl4, involving the intermediacy of a phenonium ion. Computational analysis provides insight into the reaction mechanism, especially the selectivity of phenonium opening.
Article
Chemistry, Organic
Taiga Yurino, Sunaho Saito, Mizuki Ichihashi, Takeshi Ohkuma
Summary: A Pd(OAc)(2)/P(OPh)(3) combination catalyst was used for the Tsuji-Trost-type allylic amination under aerobic conditions, and it was found that the reaction proceeded efficiently only when allylic phosphates were employed as electrophiles.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
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, Organic
Singarajanahalli Mundarinti Krishna Reddy, Subramaniyan Prasanna Kumari, Subramaniapillai Selva Ganesan
Summary: The palladium-catalyzed addition of arylboronic acid to 2-cyano-(N-aryl)-acetamide or ethyl-2-cyanoacetate followed by subsequent reaction transforms them into biologically significant derivatives. The reaction conditions are robust enough to prevent hydrolysis of the ester/amide moiety during arylation, and can also convert the unactivated nitrile moiety in acetonitrile to the corresponding acetophenone derivative.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Amrita Das, Naoto Chatani
Summary: The Rh(i)-catalysed imine-directed oxidative [3 + 2] cycloaddition of benzylamines with maleimides is reported, which can use a wide range of both substrates and achieve a successful one-pot three component strategy. Mechanistic studies suggest the formation of a zwitterionic intermediate through Rh-mediated activation of a benzylic C(sp(3))-H bond of the imine.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Min Zhang, Zhangyi Fu, Anping Luo, Xingwen Pu, Menglei Wang, Ying Huang, Yudong Yang, Jingsong You
Summary: The study presents a concise route for site-selective arylation of polycyclic aromatic hydrocarbons with easily available aryl sources, contributing to the bottom-up preparation of pi-extended PAHs. Additionally, a C8-H annulation protocol has been developed to rapidly assemble benzanthrones by simply switching the solvent to 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP).
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Zhuo Huang, Xu-Teng Liu, Ranran Cui, Qing-Wei Zhang
Summary: Activated vinylcyclopropanes can react with secondary phosphine oxides in the presence of nickel catalyst to form zwitterionic pi-allylmetal species. This asymmetric allylation reaction yields tertiary phosphine oxide products with high yields (up to 91%) and enantioselectivity (92% ee).
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Xin Liu, Yun Zhou, Xiaotian Qi, Renhe Li, Peng Liu, Guangbin Dong
Summary: A site- and regioselective vicinal di-carbo-functionalization of indoles has been realized by the palladium/norbornene (Pd/NBE) cooperative catalysis. The C1-substituted NBE plays a key role in promoting the turnover-limiting oxidative addition step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Polymer Science
Noelia Esteban, Miguel Claros, Cristina Alvarez, Angel E. Lozano, Camino Bartolome, Jesus M. Martinez-Ilarduya, Jesus A. Miguel
Summary: A new set of microporous organic polymers (POPs) with high microporosity and moderate thermal stability has been synthesized via Friedel-Crafts knitting. These polymers, containing diphosphine derivatives, act as efficient catalysts for Suzuki-Miyaura coupling reactions, exhibiting excellent recyclability.
Article
Chemistry, Physical
Ren-Xiao Liang, Chao Zhong, Zhi-Hong Liu, Miao Yang, Heng-Wei Tang, Jian-Fei Chen, Yun-Fang Yang, Yi-Xia Jia
Summary: Palladium-catalyzed intramolecular enantioselective beta-arylation of tetrasubstituted endocyclic and exocyclic enamines can lead to a range of optically active products with high enantiomeric ratios. Different bases and chiral ligands can be used to achieve different levels of enantioselectivity.
Article
Chemistry, Multidisciplinary
Zhuangli Zhu, Zhenhua Wang, Yajun Jian, Huaming Sun, Guofang Zhang, Jason M. Lynam, C. Robert McElroy, Thomas J. Burden, Rebecca L. Inight, Ian J. S. Fairlamb, Weiqiang Zhang, Ziwei Gao
Summary: The dual function and role of iron(0) pentacarbonyl [Fe(CO)(5)] have been identified in gaseous CO-free carbonylative Suzuki-Miyaura cross-couplings, where Fe(CO)(5) supplied CO in situ, leading to the propagation of catalytically active Pd-Fe nanoparticles. The developed reaction conditions are mild, do not require specialized CO high-pressure equipment, and exhibit wide functional group tolerance, yielding a library of biaryl ketones in good yields.
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
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, Multidisciplinary
Cleve D. Mboyi, Didier Poinsot, Julien Roger, Katia Fajerwerg, Myrtil L. Kahn, Jean-Cyrille Hierso
Summary: The review discusses the production of hydrogen from ammonia borane using nanoparticle-based catalysts, highlighting the importance of catalyst preparation, control, and understanding of electronic structures. Various transition metals are examined for their cost, availability, and performance in hydrogen production.
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.
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
Fuying Zhu, Yamei Lin
Summary: In this study, a low-metal iron-supported catalyst (Fe20/NC-Mg) was reported for the efficient synthesis of quinoxaline compounds, using water as a solvent and without additional bases. The synergistic effect of FeNx site and Mg (OH)2 nanorods in the catalyst played a key role in achieving high yields (82-91%) in 16 examples. The gram-level synthesis and reusability of the catalysts after four cycles demonstrated its industrial application potential.
Article
Chemistry, Organic
Mikhail Kozlov, Alexey Tyurin, Andrey Dmitrenok, Vyacheslav Rusak, Aleksander Fedorov, Igor Zavarzin, Yulia Volkova
Summary: This study presents a novel and practical synthesis method for phosphorus-substituted 1,3,4-thiadiazolines using phosphorylthioformic acid hydrazides and ketones. The protocol demonstrates operational simplicity, availability of reagents, and tolerance towards different functional groups.
Article
Chemistry, Organic
Jisna Jose, Thomas Mathew
Summary: 2-Cyclopentenone and its derivatives are highly esteemed synthetic intermediates with exceptional utility in organic synthesis. They are favored structural motifs in numerous pharmaceutical drugs and natural products, highlighting their significance. The review discusses the various methods used to synthesize cyclopentenones from 2016 to 2023.