Article
Chemistry, Multidisciplinary
Mathis J. Benedikter, Janis V. Musso, Wolfgang Frey, Roman Schowner, Michael R. Buchmeiser
Summary: Despite their excellent selectivities and activities, Mo- and W-based catalysts for olefin metathesis have not been widely used due to their air sensitivity. The synthesized cationic-at-metal molybdenum and tungsten imido alkylidene NHC nitrile complexes are stable in air and can catalyze olefin metathesis reactions without prior activation. The presence of a nitrile ligand is crucial for their stability, while variations in imido and anionic ligands affect reactivities and stability.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Physical
Augustin Nouaille, Jan Lorkowski, Xavier Pannecoucke, Marc Mauduit, Thomas Poisson, Samuel Couve-Bonnaire
Summary: This article presents a review of the challenges in using fluoroalkenes in ring-closing metathesis and cross-metathesis, highlighting the major developments in this field in recent years.
Article
Chemistry, Multidisciplinary
Julius Hillenbrand, J. Nepomuk Korber, Markus Leutzsch, Nils Noethling, Alois Fuerstner
Summary: Molybdenum alkylidyne complexes with a trisilanolate podand ligand framework are highly selective catalysts for alkyne metathesis, with complex 1a being the most reactive but requiring high loadings in certain applications. These catalysts decompose readily via a bimolecular pathway, but increasing the size of peripheral substituents on silicon can largely avoid this rapid degradation.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Polymer Science
Janis V. Musso, Paul Gebel, Vincent Gramm, Wolfgang Frey, Michael R. Buchmeiser
Summary: A system for visible-light-controlled ring-opening metathesis polymerization (ROMP) was developed by combining thermally latent group 6 olefin metathesis initiators with a photoredox catalyst. This system can be applied to two-dimensional (2D) photolithography, and it exhibits high activity and stability without the need for thermal or UV post-curing.
Article
Chemistry, Multidisciplinary
Ren Wei Toh, Michal Patrzalek, Tomasz Nienaltowski, Jakub Piatkowski, Anna Kajetanowicz, Jie Wu, Karol Grela
Summary: The development of continuous-flow reactors has attracted attention in the synthetic community, offering a safe and easy scaling-up alternative compared to batch reactors. By demonstrating a flow setup for ring-closing metathesis and reducing ruthenium contamination through soluble metal scavenger, the method shows potential for industrial usage. An upscale process for a Sildenafil analogue in continuous-flow fashion was achieved through adjusting tubing size and flow rate.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(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)
Review
Chemistry, Multidisciplinary
Atitegeb Abera Tsedalu
Summary: Olefin metathesis is a metal-mediated C-C bond exchange reaction that is widely used in the synthesis of organic compounds, polymers, drugs, plastics, and other synthetic materials. It involves breaking the double bond of an olefin precursor to redistribute the fragments and obtain new products.
JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Mami Miyairi, Tsuyoshi Taniguchi, Tatsuya Nishimura, Katsuhiro Maeda
Summary: Improved methods for the synthesis of linear and cyclic poly(diphenylacetylene)s using MoCl5- and WCl4-based catalytic systems have been developed. MoCl5 induces migratory insertion polymerization of diphenylacetylenes in the presence of arylation reagents such as Ph4Sn and (ArSnBu3)-Bu-n to produce cis-stereoregular linear poly(diphenylacetyelene)s with high molecular weights. On the other hand, WCl4 induces ring expansion polymerization of diphenylacetylenes in the presence of Ph4Sn or reducing reagents to produce cis-stereoregular cyclic poly(diphenylacetylene)s with high molecular weights. Both catalytic systems are applicable to the polymerization of various diphenylacetylenes having polar functional groups such as esters that are not efficiently polymerized by conventional methods.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Inorganic & Nuclear
Paulina Guerrero-Almaraz, Manuel Quiroz, Joseph H. Reibenspies, Marcetta Y. Darensbourg
Summary: Two synthetic approaches were used to install metallodithiolate ligands on molybdenum centers, resulting in a trimetallic dication, CoMoCo', with unique structure and characteristics, including bisnitrosylation and the generation of unpaired electrons.
INORGANIC CHEMISTRY
(2021)
Article
Green & Sustainable Science & Technology
Fan Guo, Xiaoli Xi, Liwen Ma, Zuoren Nie
Summary: This study proposes a recyclable clean separation technology for tungsten and molybdenum using a porous amine resin. The resin exhibited a high sorption capacity and good cycle performance, and the separation of tungsten and molybdenum was achieved through ion exchange and chemical binding. This technology has significant implications for waste recovery.
JOURNAL OF CLEANER PRODUCTION
(2022)
Article
Chemistry, Physical
Tatiana Otroshchenko, Qiyang Zhang, Evgenii Kondratenko
Summary: The study explores an efficient method for propene generation from ethylene and 2-butene using modified SiO2 support, with the addition of phosphorous facilitating the creation of a special type of hydroxyls to aid in 2-butene adsorption on MoOx and facilitate the conversion to Mo = CH-CH3.
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, Multidisciplinary
Shingo Machida, Ken-ichi Katsumata, Kei Maeda, Atsuo Yasumori
Summary: This study investigated the effect of vanadium oxide on the crystallization of CaO-Al2O3-SiO2 (CAS) glasses. It was found that the addition of vanadium oxide controlled the aspect ratio of layered crystals in the glass and a new nucleation agent for the precipitation of metastable CaAl2Si2O8 in CAS glass was developed. The results showed that the addition of a relatively small content of vanadium oxide increased the aspect ratio of metastable CaAl2Si2O8 particles and no crystallization occurred without metallic Mo particles.
Article
Chemistry, Physical
Or Eivgi, Anna Vaisman, N. Gabriel Lemcoff
Summary: The ligand shell that surrounds an active metal center plays a crucial role in determining the reactivity and properties. This study presents new ruthenium indenylidene complexes with a combination of phosphite olefin metathesis precatalysts and cyclic alkyl amino carbene (CAAC) ligands, which show efficient photoactivity and robust stability. These catalysts exhibit formidable latency at ambient temperatures, allowing for a wide range of olefin metathesis reactions and efficient recycling for multiple reaction cycles under air.
Article
Chemistry, Physical
Luciana Sarmento Fernandes, Dalmo Mandelli, Wagner A. Carvalho, Cedric Fischmeister, Christian Bruneau
CATALYSIS COMMUNICATIONS
(2020)
Article
Chemistry, Physical
Gabriel M. Vieira, Artur V. Granato, Elena V. Gusevskaya, Eduardo N. dos Santos, Pierre H. Dixneuf, Cedric Fischmeister, Christian Bruneau
APPLIED CATALYSIS A-GENERAL
(2020)
Review
Chemistry, Physical
Hallouma Bilel, Naceur Hamdi, Cedric Fischmeister, Christian Bruneau
Article
Chemistry, Organic
Harikrishnan Jayaprakash, Liwei Guo, Shengdong Wang, Christian Bruneau, Cedric Fischmeister
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2020)
Review
Chemistry, Inorganic & Nuclear
Rafael Gramage-Doria, Christian Bruneau
Summary: Ruthenium complexes are widely recognized as excellent pre-catalysts for challenging C-H bond functionalization reactions, and their combination with other types of chemical reactions can reduce purification and isolation steps, increasing reaction sustainability. Research in this field focuses on the compatibility of different reaction sequences, with a particular emphasis on the compatibility of ruthenium-catalyzed C-H bond functionalization with organic transformations, metal-mediated reactions, and transition metal catalysis.
COORDINATION CHEMISTRY REVIEWS
(2021)
Editorial Material
Chemistry, Inorganic & Nuclear
Jean-Francois Soule, Christian Bruneau, Christophe Darcel
Review
Chemistry, Multidisciplinary
Salekh M. Masoud, Dania V. Vorobyeva, Dmitry A. Petropavlovskikh, Christian Bruneau, Sergey N. Osipov
Summary: This review summarizes literature data on methods for introducing fluorine atoms and fluoralkyl groups into different ligands to construct metathesis-active ruthenium carbene complexes, analyzing their influence on catalytic activity. The choice of fluorinated substituents in NHC ligands aims to increase ruthenium atom electrophilicity and enhance complex activity; introducing polyfluoroalkyl groups can help solve the issue of catalyst recovery.
RUSSIAN CHEMICAL REVIEWS
(2021)
Article
Chemistry, Physical
Luciana Sarmento Fernandes, Dalmo Mandelli, Wagner A. Carvalho, Elsa Caytan, Cedric Fischmeister, Christian Bruneau
Summary: The direct functionalization of sterically demanding alpha,alpha-disubstituted double bonds in beta-pinene, (-)-limonene and (-)-limonene terpenoids has been achieved through cross metathesis with internal olefins. This clean transformation provides a new method for accessing functionalized bulky cyclic terpenes, where the terminal double bond generates a trisubstituted olefin.
APPLIED CATALYSIS A-GENERAL
(2021)
Article
Biochemistry & Molecular Biology
Thalita S. Galhardo, Anderson K. Ueno, Thais A. Costa-Silva, Andre G. Tempone, Wagner A. Carvalho, Cedric Fischmeister, Christian Bruneau, Dalmo Mandelli, Joao Henrique G. Lago
Summary: In this study, compounds isolated from N. leucantha were used as starting material to synthesize two new derivatives, which showed activity against trypanosome and no toxicity to mammalian cells. Mechanism study revealed that the derivatives caused depolarization of the parasite's plasma membrane and collapse of mitochondrial membrane potential. Therefore, this compound could be a potential candidate for future drug design in the treatment of Chagas disease.
CHEMICO-BIOLOGICAL INTERACTIONS
(2022)
Article
Chemistry, Physical
Thalita S. Galhardo, Anderson K. Ueno, Wagner A. Carvalho, Thais A. Costa-Silva, Marina M. Goncalves, Mariana B. Abiuzi, Andre G. Tempone, Joao Henrique G. Lago, Dalmo Mandelli, Cedric Fischmeister, Christian Bruneau
Summary: Ruthenium-catalyzed cross metathesis of biseugenol with electron-deficient olefins resulted in the synthesis of derivatives 3a-3e in good yields and excellent conversion rates. The antitrypanosomal activity of these compounds against Trypanosoma cruzi was evaluated, and compounds 3b and 3d showed similar IC50 values to biseugenol, but with reduced toxicities and similar selectivity indexes to the standard drug benznidazol.
Article
Chemistry, Physical
Naba Abuhafez, Herve Ruffin, Raghu Kamaraj, Christian Bruneau, Rafael Gramage-Doria
Summary: A new method for the synthesis of 1,3-diene building blocks using ruthenium-catalyzed oxidative homo- and cross-coupling is reported, which mainly produces the E,E isomer. This methodology also allows for the synthesis of adipic acid ester derivatives in a one-pot fashion after in situ ruthenium-catalyzed hydrogenation.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Physical
Julien Hervochon, Vincent Dorcet, Kathrin Junge, Matthias Beller, Cedric Fischmeister
CATALYSIS SCIENCE & TECHNOLOGY
(2020)