Article
Chemistry, Multidisciplinary
Tobias Biberger, Nils Noethling, Markus Leutzsch, Christopher P. Gordon, Christophe Coperet, Alois Fuerstner
Summary: In the investigation of ruthenium precatalysts used for light-driven alkyne gem-hydrogenation reactions, a thermally robust anionic dinuclear sigma-dihydrogen complex was found. This complex, formed by the reaction of [(IPr)(eta(6)-cymene)RuCl2] with H-2 under UV-irradiation, is a rare example of anionic sigma-complexes lacking any structural attributes to counterbalance the negative charge and prevent metal center insertion into ligated H-2.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Adrian Sytniczuk, Filip Struzik, Vishal Purohit, Karol Grela, Anna Kajetanowicz
Summary: The synthesis of inexpensive 2-isopropyl-6-methylaniline analogues was achieved through the employment of aza-Claisen rearrangement and subsequent reduction of anilines, overcoming the issue of high price and low availability. The obtained aniline derivatives were utilized in the synthesis of lipophilic Hoveyda-Grubbs-type complexes, serving as efficient catalysts in ethenolysis reactions. The complexes with bulky sec-butyl substituent exhibited superior performance compared to the leading catalyst based on 2-isopropyl-6-methylaniline, making them valuable candidates for large-scale industrial production with a TON of up to 192,000.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Physical
Thais R. Cruz, Gustavo H. C. Masson, Kelly A. E. Amorim, Antonio E. H. Machado, Beatriz E. Goi, Valdemiro P. Carvalho-Jr
Summary: We synthesized metal complexes of Ru and Pd and characterized them through various analytical techniques. Additionally, we discovered that Ru/Pd can polymerize norbornene through two different mechanisms, achieving high yields. This finding is of significant importance for the development of new efficient catalysts.
Article
Chemistry, Multidisciplinary
Saswata Gupta, Siyuan Su, Yu Zhang, Peng Liu, Donald J. Wink, Daesung Lee
Summary: Metallaaromatics are a unique class of aromatic compounds incorporating one or more transition metal elements, showing distinctive structural and theoretical interests, and serving as a novel platform for new catalyst development.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Laurence N. Rohde, Therese H. Wild, Steven T. Diver
Summary: In this study, a variety of ene-yne cross metathesis reactions were carried out using unsaturated phosphonate and phosphate reagents, resulting in the phosphorylated 1,3-diene products in good to excellent yields. The challenging ene-yne metatheses were facilitated by a Grubbs catalyst with a cyclic amino alkyl carbene ligand, allowing for the transformation of terminal alkynes of varying substitution into conjugated diene products with high yields. The resulting dienes were further modified through Horner-type Wittig reactions and a Diels-Alder cycloaddition.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Multidisciplinary Sciences
Shiran Aharon, Dan Meyerstein, Eyal Tzur, Dror Shamir, Yael Albo, Ariela Burg
Summary: This study developed a single-stage process for the entrapment of ruthenium-based catalysts using the sol-gel process, with results showing that the nature of the precursor affects pore size and catalyst activity, and matrices prepared with tetraethoxysilane at an alkaline pH exhibit a better reaction rate. This research is the first to present a one-step process simpler and faster than methods reported in the literature for catalyst entrapment by the sol-gel process under standard conditions.
SCIENTIFIC REPORTS
(2021)
Article
Green & Sustainable Science & Technology
Han Sun, Tao Wu, Stephenie Hiu Yuet Chen, Yuanyuan Ren, Shufang Yang, Junchao Huang, Haijin Mou, Feng Chen
Summary: This review discusses valid approaches and powerful tools in microalgae cultivation, including kinetic models, metabolic flux analysis, and genetic tools. These methods and tools can enhance the efficiency and value of microalgae production, maximizing biomass generation.
RENEWABLE & SUSTAINABLE ENERGY REVIEWS
(2021)
Review
Chemistry, Organic
Jennifer Morvan, Antonio Del Vecchio, Jakub Talcik, Dylan Bouetard, Marc Mauduit
Summary: Asymmetric Olefin Metathesis (AOM) is a highly versatile synthetic tool for producing chiral building blocks with excellent enantiopurity. Catalysts that can control both the Z-selectivity and enantioselectivity of metathesis transformations are in high demand due to the ubiquity of Z-alkene moiety in natural products. This review comprehensively covers all the breakthroughs achieved in the challenging field of Z-enantioselective olefin metathesis, which is important in the total synthesis of complex molecules.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Augustin Nouaille, Xavier Pannecoucke, Thomas Poisson, Samuel Couve-Bonnaire
Summary: This study presents an efficient ruthenium-catalyzed CM reaction method, successfully allowing various alkenes to react with methyl 2-fluoroacrylate to obtain trisubstituted fluoroalkenes for the first time. Additionally, an unprecedented TON value for the CM reaction involving fluoroalkenes was achieved, demonstrating good tolerance and effectiveness with a wide range of olefin partners.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Shaofeng Li, Shijie Feng, Yali Zhou, Chao Liu, Bo Chen, Xiangyou Xing
Summary: Asymmetric olefin metathesis is a powerful strategy for stereocontrolled synthesis, and this study introduces a new series of cyclometalated stereogenic-at-Ru catalysts that enable highly efficient asymmetric ring opening/cross-metathesis (AROCM) and asymmetric ring-closing metathesis (ARCM) reactions. These catalysts can be easily accessed with either right-handed or left-handed configurations at the Ru center. The right-handed chiral Ru catalysts enable the synthesis of densely functionalized cyclopentanes with excellent stereo- and enantioselectivities, while the left-handed chiral Ru catalysts facilitate the production of cyclic ethers and amides with tertiary or quaternary carbon stereocenters with high enantioselectivities.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Multidisciplinary
Julien Monot, Enrico Marelli, Blanca Martin-Vaca, Didier Bourissou
Summary: The chemistry of (P,C)-cyclometalated complexes derived from naphthyl phosphines [(Np)(P,C)M] is reviewed and analysed in this paper. The three main synthetic approaches, P-chelation assisted C-H activation, oxidative addition and transmetalation, are described and compared. These complexes exhibit high thermal and chemical robustness, and have been shown to be competent catalysts in various transformations, as well as key intermediates in others.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Multidisciplinary Sciences
Agata Tyszka-Gumkowska, Vishal B. Purohit, Tomasz Nienaltowski, Michal Dabrowski, Anna Kajetanowicz, Karol Grela
Summary: In this study, diverse polyfunctional substrates were subjected to olefin metathesis reactions in water emulsions using hydrophobic ruthenium catalysts. Instead of using surfactants, ultrasound and microwave techniques were tested on a small scale while conventional heating and mechanical stirring were effective on a larger scale. The developed conditions allowed for low catalyst loadings and simple isolation and purification of the products. The synthetic protocol was successfully applied in the large-scale synthesis of a pharmaceutically related product, sil-denafil (Viagra) derivative.
Article
Chemistry, Physical
Iakov S. Fomenko, Artem A. Mikhailov, Vasily Vorobyev, Natalia V. Kuratieva, Gennadiy A. Kostin, Dominik Schaniel, Vladimir A. Nadolinny, Artem L. Gushchin
Summary: This work focuses on the preparation and photochemical investigations of a novel binuclear heterometallic complex, which exhibits a bifunctional platform capable of releasing nitric oxide in solution and reversibly switching the NO ligand coordination in the solid state. The presence of vanadium strongly influences the photochemical properties of ruthenium nitrosyl in both solid and solution phases, as confirmed by various analytical techniques.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Pavel A. Kumandin, Alexandra S. Antonova, Roman A. Novikov, Kirill A. Vasilyev, Marina A. Vinokurova, Mikhail S. Grigoriev, Anton P. Novikov, Daria K. Polianskaia, Kirill B. Polyanskii, Fedor I. Zubkov
Summary: This study investigates the synthesis and catalytic activity of ruthenium chelates with various heteroatoms in a six-membered ring. The researchers successfully prepared second-generation Hoveyda-Grubbs-type catalysts with a sulfur-ruthenium coordinate bond using standard procedures. They found that the trans-isomers of these catalysts showed excellent catalytic activity, outperforming the commercially available HG-II catalyst.
Review
Chemistry, Multidisciplinary
Cong Han, Qian Li, Haishuo Ji, Wenping Xing, Limin Zhang, Liyun Zhang
Summary: Aptamers, similar to antibodies, are chemical molecules that can be used in various virus detection sensors. They can be mainly classified into optical and electronic aptasensors based on the type of transducer.
CHEMISTRY-AN ASIAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Paul Zaby, Jan Blasius, Anna K. Mueller, Steven P. Nolan, Oldamur Holloczki
Summary: The formation mechanism of metal-N-heterocyclic carbene (NHC) complexes from imidazolium salts in the presence of weak bases was investigated through theoretical methods. Quantum chemical calculations revealed that both sodium acetate and trimethylamine facilitate complex formation. Molecular dynamics simulations showed that the ionic nature of the [AuCl2](-) and imidazolium ions, as well as the sodium acetate base, keep these species associated in the reaction mixture through ion pairing. The neutral amine, however, remains mostly separated from the other reaction partners, making it a significantly less effective base.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Xinyuan Ma, Manoj V. Mane, Luigi Cavallo, Steven P. Nolan
Summary: An efficient method for the regioselective 1,2-hydrosilylation of N-heteroarenes using silanes as hydride donors is described. The versatile catalyst [RuCl(PPh3)(2)(eta(5)-(3-phenylindenylidene))] is employed for the first time in this catalytic reaction, displaying high efficiency at low loading and mild conditions. The mechanism of this transformation is investigated through stoichiometric reactions and DFT calculations.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Editorial Material
Chemistry, Multidisciplinary
Paul Zaby, Jan Blasius, Anna K. K. Mueller, Steven P. P. Nolan, Oldamur Holloczki
Summary: In this issue, Oldamur Hollczki and co-workers from the Universities of Bonn, Ghent and Debrecen are featured on the cover. The image showcases the quest for an ionic base that can combine with the acidic proton of an imidazolium cation to form a carbene complex. For the full article, visit 10.1002/chem.202203636.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Jennifer Morvan, Dylan Bouetard, Lingyu Kong, Yajie Chou, Thomas Vives, Muriel Albalat, Thierry Roisnel, Christophe Crevisy, Paola Nava, Stephane Humbel, Nicolas Vanthuyne, Herve Clavier, Marc Mauduit
Summary: A set of 16 chiral ruthenium complexes with atropisomerically stable N-Heterocyclic Carbene (NHC) ligands were synthesized. Among them, (atrop)BIAN-NHC Ru-catalyst showed the highest activity (up to 97 : 3 enantiomeric ratio) in asymmetric ring-opening-cross metathesis (AROCM) and was further converted to a Z-selective catechodithiolate complex. This complex exhibited high efficiency in Z-selective AROCM of exo-norbornenes, producing trans-cyclopentanes with excellent Z-selectivity (>98%) and high enantioselectivity (up to 96.5 : 3.5 enantiomeric ratio).
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Sebastien G. Guillet, Ishfaq Ibni Hashim, Marek Belis, Kristof Van Hecke, Catherine S. J. Cazin, Steven. P. Nolan
Summary: A simple synthetic method for synthesizing various [Rh(acac)(CO)(NHC)] complexes is presented. In situ infrared monitoring provides valuable information on the reaction mechanism, including the identification of a crucial intermediate. Understanding the reaction mechanism has led to the discovery of novel pathways to commonly used congeners.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Sebastien G. Guillet, Aleksei A. Logvinov, Vladislav A. Voloshkin, Ekaterina A. Martynova, Steven P. Nolan
Summary: Researchers report a simple method for the synthesis of azetidines from 2-isoxasoline-3-carboxylates and alkenes, using [Au(cbz)(NHC)] complexes as photocatalysts. The reaction is applicable to a wide range of substrates. Mechanistic studies confirm the energy transfer pathway. This study further expands the potential application of gold catalysts in energy transfer chemistry and catalysis.
Article
Chemistry, Physical
David C. Cabanero, Jennifer A. Nguyen, Catherine S. J. Cazin, Steven P. Nolan, Tomislav Rovis
Summary: A system has been developed that uses deep red to near-infrared light to activate a latent ruthenium olefin metathesis catalyst. This is achieved by using an osmium(II) photocatalyst that is excited to its triplet state and a latent solvent-coordinated, cationic precatalyst that undergoes excited-state single-electron reduction. The system demonstrates excellent spatiotemporal control under light irradiation and shows improved light penetration through barriers.
Review
Chemistry, Multidisciplinary
Thomas Scattolin, Giovanni Tonon, Eleonora Botter, Sebastien G. Guillet, Nikolaos V. Tzouras, Steven P. Nolan
Summary: The review focuses on the design of gold-based synthons that enable the synthesis of target complexes through simple steps under mild conditions. Mechanistic aspects of their synthesis and reactivity, as well as applications as efficient pre-catalysts, antitumor agents, and photo-emissive materials, are discussed.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Shiyi Yang, Xiang Yu, Yaxu Liu, Michele Tomasini, Lucia Caporaso, Albert Poater, Luigi Cavallo, Catherine S. J. Cazin, Steven P. Nolan, Michal Szostak
Summary: The Suzuki-Miyaura cross-coupling reaction enables the construction of biaryl ketones from inert amide bonds. However, the mechanism of C(acyl)-N bond oxidative addition and catalyst effect in this reaction remain poorly understood. This study investigates the use of [Pd(NHC)(sulfide)Cl-2] catalysts for amide N-C bond activation and presents the reaction development, kinetic studies, and reaction scope. DFT studies were also conducted to gain insight into the mechanism of C(acyl)-N bond oxidative addition and catalyst activation. The results suggest that [Pd(NHC)(sulfide)Cl-2] precatalysts could find application in C(acyl)-X bond activation in organic synthesis and catalysis.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Xinyuan Ma, Steven P. Nolan
Summary: The first-generation ruthenium-indenylidene olefin metathesis complex catalyzes the 1,2-hydrosilylation reaction to produce dihydroquinoline derivatives with high regioselectivity. The complex shows excellent catalytic efficiency when the challenging Ph2SiH2 hydride donor is used. The reaction is efficient with low catalyst loadings and applicable to a wide range of quinoline derivatives and N-heterocycles. A proposed mechanism for this transformation is based on stoichiometric reactions.
Article
Chemistry, Inorganic & Nuclear
Thomas Scattolin, Aleksei A. Logvinov, Nikolaos V. Tzouras, Catherine S. J. Cazin, Steven P. Nolan
Summary: N-heterocyclic carbene (NHC) ligands have evolved from being lab curiosities to important supporting ligands in various fields such as organometallic chemistry, homogeneous catalysis, medicinal chemistry, and materials science.
Article
Chemistry, Multidisciplinary
Sylwia Ostrowska, Pierre Arnaut, David J. Liptrot, Catherine S. J. Cazin, Steven P. Nolan
Summary: The synthesis, isolation, and full characterization of a new copper complex [Cu(IPr)(OC(H)(CF3)(2))] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) are reported. This copper(I) complex is a versatile synthon capable of activating various X-H bonds including C-H, N-H, and S-H bonds. [Cu(IPr)(OC(H)(CF3)(2))] was investigated as a pre-catalyst in several catalytic reactions.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Raphael Gauthier, Nikolaos V. Tzouras, Steven P. Nolan, Jean-Francois Paquin
Summary: The gold-catalyzed hydration of 2,2,2-trifluoroethyl-substituted alkynes exhibits high regioselectivity, resulting in the formation of β-trifluoromethylketones as the major products. This transformation highlights the significant directing effect of the trifluoromethyl group, mediated by its inductive effect, in gold-catalyzed addition to alkynes.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Vladislav A. Voloshkin, Yaxu Liu, Marek Belis, Min Peng, Kristof Van Hecke, Catherine S. J. Cazin, Steven P. Nolan
Summary: The synthesis of novel phosphine palladium PEPPSI and dimer complexes bearing RuPhos, SPhos and XPhos phosphines is reported. The crystal structures of XPhos Pd PEPPSI with pyridine, SPhos Pd PEPPSI with 3-chloropyridine as throw-away ligands and the RuPhos palladium dimer were obtained and compared with previously reported congeners. The catalytic activity of these complexes was examined via a C-N coupling reaction, and it was found that RuPhos complex 2b showed the highest catalytic activity with 97% yield at a low catalyst loading. The addition of 3-pentanone significantly improved the yields of phosphine dimers and PEPPSI complexes when the reactions were performed in THF.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Benon Maliszewski, Eleonora Casillo, Perrine Lambert, Fady Nahra, Catherine Cazin, Steven Nolan
Summary: This article reports an efficient olefin hydrosilylation protocol using Pt(ii)-thioether-based pre-catalysts. These simple and readily available complexes exhibit excellent catalytic performance and offer significant advantages over existing alternatives, enabling rapid and high conversions at ppm-level catalyst loadings.
CHEMICAL COMMUNICATIONS
(2023)
Review
Chemistry, Multidisciplinary
Dan He, Yawen Li, Fuwen Zhao, Yuze Lin
Summary: High trap density in organic solar cells leads to localized charge carriers and reduced carrier lifetime, limiting device efficiency. This feature article summarizes the recent advances of trap suppression by material design and device engineering.
CHEMICAL COMMUNICATIONS
(2024)
Review
Chemistry, Multidisciplinary
Olivier Monfort, Arshitha Madhusudhan, Martin Motola
Summary: This article presents the advantages of coupling photocatalysis and Fenton-based processes for environmental remediation and discusses their synergy. It critically examines the simultaneous triggering of these two processes and provides insights into research approaches. The study aims to enhance understanding of this complex process and highlight the potential integration of new catalysts in current wastewater treatment technology.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Manideepa Dhar, Chittaranjan Mishra, Avijit Das, Uttam Manna
Summary: An approach of 'polymerization of monomers in its aggregated form' has been introduced to tailor the water wettability of fibrous and porous substrates, achieving hydrophobicity to superhydrophobicity transition, as well as patterned wettability. This facile chemical method provides a durable coating with adjustable and patterned wettability for various potential applications.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Saswat Ranjan Bhoi, Chhanda Debnath, Shikha Gandhi
Summary: In this article, a novel catalytic reaction using Pd(0) and Bronsted acid is reported for the synthesis of biologically important imidazolidinone-fused N-heterocycles through redox-neutral intramolecular N-allylation of indoles and pyrroles with alkynes. This atom-economical method is applicable to a wide range of substrates and eliminates the need for leaving groups or oxidizing agents commonly used in traditional allylation reactions.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Longkun Chen, Mingshuai Zhang, Meichen Liu, Zhuoyuan Liu, Yuetong Qiu, Zhilai Zhang, Fuchao Yu, Jiuzhong Huang
Summary: In this study, an efficient Rh(III)-catalyzed selective mono- and dual-C-H bond functionalization/cyclization with iodonium ylide as the sole coupling partner was demonstrated. Fused benzodiazepine skeletons were obtained in excellent yields, providing an improved approach to dual C-H unsymmetrical functionalization.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Alice Kennett, Sven Epple, Gabriella van der Valk, Irene Georgiou, Evelyne Gout, Romain R. Vives, Angela J. Russell
Summary: This study presents the design and synthesis of sulfated disaccharide inhibitors based on IdoA(2S)-GlcNS(6S), which showed potent inhibition of Sulf-2. The results suggest that IdoA(2S)-GlcNS(6S) is the shortest fragment size required for effective inhibition of Sulfs, and a trisulfated disaccharide is identified as the minimal fragment size of heparan sulfate for effective endosulfatase inhibition.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Mauro Garbini, Andrea Brunetti, Riccardo Pedrazzani, Magda Monari, Massimo Marcaccio, Giulio Bertuzzi, Marco Bandini
Summary: The self-adaptability of galvanostatic electrolysis was found to be helpful in a multistage chemo- and diastereoselective electrochemically promoted cyclodimerization of chalcones. Through a series of reductive events, densely functionalized cyclopentanes with five contiguous stereocenters were obtained (25 examples, yields up to 95%, dr values up to >20:1). Further experimental and electrochemical investigations indicated the crucial role of dynamic kinetic resolution of the aldol intermediate in the reaction mechanism.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Dhananjay S. Nipate, Neha Meena, Prakash N. Swami, Krishnan Rangan, Anil Kumar
Summary: In this study, the synthesis of functionalized benzo[a]phenazines and indazolo[2,3-a]quinolines was achieved through Rh(III)-catalyzed oxidative annulation of 2-arylquinoxalines and 2-aryl-2H-indazoles with allyl alcohols. The method showed a wide substrate scope, excellent functional group tolerance, good to high yields of annulated products, and the capability for scaled-up synthesis. A tentative mechanism of the annulation reaction was proposed based on a preliminary mechanistic investigation.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Ruonan Zhang, Abudukadi Tudi, Xia Yang, Xuping Wang, Zhihua Yang, Shujuan Han, Shilie Pan
Summary: A new lead tellurium borate material with a unique fundamental building block [B4O10] was synthesized and found to exhibit high birefringence. The structure-property relationship was discussed using first-principles calculations.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Amresh Kumar Singh, Baishali Thakurta, Anupam Giri, Monalisa Pal
Summary: This study introduces three key concepts for the quick synthesis of large-scale high-quality 2D materials films and their utilization in device fabrication.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Reina Hagiwara, Shun Nishimura, Kosuke Okeyoshi
Summary: A copolymer-conjugated nanocatalytic system has been developed to improve electron transfer and enhance photoinduced H2 generation.
CHEMICAL COMMUNICATIONS
(2024)
