Article
Chemistry, Multidisciplinary
Kenta Mori, Midori Akiyama, Ko Inada, Yutaka Imamura, Yuichiro Ishibashi, Yusuke Takahira, Kyoko Nozaki, Takashi Okazoe
Summary: By introducing a seven-membered N-heterocyclic carbene (NHC) ligand, a significant increase in catalyst turnover number (TON) was achieved in the cross-metathesis of tetrafluoro-ethylene (TFE) and vinyl ethers. This study provides a new approach to enhance catalytic efficiency in such reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Anas Semghouli, Attila M. Remete, Lorand Kiss
Summary: Novel functionalized fused-ring β-amino lactones and lactams with multiple chiral centers were synthesized from readily available strained bicyclic β-amino acids via a stereocontrolled synthetic route. The key step involved ring-rearrangement metathesis of allyl/propargyl esters or N-allylated/N-propargylated amides of (oxa)norbornene β-amino acids. The RRM transformations were investigated using commercially available catalysts. Importantly, the procedure did not alter the configurations of the chiral centers, meaning that the starting (oxa)norbornene β-amino acids predetermined the configuration of the formed products.
Article
Chemistry, Multidisciplinary
Jun Zhu, Rui Zhang, Guangbin Dong
Summary: A rare reversible C-C single-bond metathesis reaction catalyzed by ruthenium was reported, enabling the synthesis of biaryl compounds under redox-neutral and pH-neutral conditions. The reaction mode involves unexpected 18-electron closed-shell intermediates and is expected to inspire the development of more general C-C single-bond metathesis and orthogonal cross-coupling reactions.
Article
Polymer Science
Mika Kojima, Xiuxiu Wang, Lance O'Hari P. Go, Ryoji Makino, Yuichi Matsumoto, Daisuke Shimoyama, Mohamed Mehawed Abdellatif, Joji Kadota, Seiji Higashi, Hiroshi Hirano, Kotohiro Nomura
Summary: High molecular weight polyesters were synthesized by ADMET polymerization and subsequent hydrogenation, leading to improved tensile properties in the case of HP1 from M1 as the molar mass increased.
Article
Chemistry, Applied
Ravindra S. Phatake, Noy B. Nechmad, Ofer Reany, N. Gabriel Lemcoff
Summary: A selective ring-closing metathesis (RCM) reaction using latent sulfur chelated ruthenium iodide benzylidenes as catalysts, activated by thermal and photochemical stimuli, has been reported. This method enables the formation of large macrocycles with high yields, especially for dienes with one terminal alkene and one internal double bond. For substrates containing two internal double bonds, a sacrificial methylene donor can be used to obtain the desired products.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
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
Christopher C. McAtee, Daniel J. Nasrallah, Ho Ryu, Michael R. Gatazka, Rory C. McAtee, Mu-Hyun Baik, Corinna S. Schindler
Summary: We describe a regioselective Lewis-acid-catalyzed method for the synthesis of highly functionalized cyclopentadienes incorporating diverse subunits. Insightful studies suggest that the mechanism involves Lewis-acid-catalyzed cycloadditions followed by stepwise oxetane fragmentation, resulting in the formation of functionalized cyclopentadienes. This work provides new insights into the design of catalytic carbonyl-olefin metathesis reactions.
Article
Chemistry, Multidisciplinary
Xiuxiu Wang, Weizhen Zhao, Kotohiro Nomura
Summary: By using RuCl2(IMesH2)(CH-2-OiPr-C6H4) catalyst, ADMET polymerization of bis(undec-10-enoate) and isosorbide in ionic liquids at 50°C resulted in higher molecular weight polymers compared to previous reports. However, degradation of the polymer was observed upon scaling up the reaction. Tandem hydrogenation of the unsaturated polymer in a [Bmim]PF6-toluene biphasic system produced the corresponding saturated polymer.
Article
Chemistry, Physical
Leonildo A. Ferreira, Josiane T. Silva, Raissa G. Alves, Kelley C. B. Oliveira, Eduardo N. dos Santos
Summary: In this study, the cross metathesis of estragole and methyl sorbate was investigated to produce methyl 6-(4-methoxyphenyl)hexa-2,4-dienoate with good conversion and selectivity using ruthenium-based metathesis catalysts at low catalyst loadings as 50 ppm (0.005 mol%) and minimal solvent. This demonstrates the importance of catalyst selection and reaction conditions in achieving the desired product conversion and selectivity.
APPLIED CATALYSIS A-GENERAL
(2021)
Article
Chemistry, Multidisciplinary
Manhao Zeng, Yu-Hsuan Lee, Garrett Strong, Anne M. LaPointe, Andrew L. Kocen, Zhiqiang Qu, Geoffrey W. Coates, Susannah L. Scott, Mahdi M. Abu-Omar
Summary: This study demonstrates a new approach for recycling polyethylene plastic, upgrading it to higher value-added divinyl oligomers with high yields through a sequence of reactions. The three-step process is economically viable on an industrial scale, converting discarded polyethylene into value-added chemicals for various applications.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2021)
Article
Chemistry, Multidisciplinary
Stella A. Gonsales, Zoe C. Mueller, Fengyue Zhao, Paulo H. S. Paioti, Lydia Karmazin, Jing Wan, Fang Liu, K. N. Houk, Amir H. Hoveyda
Summary: The study reveals that phosphine-free Ru-CAAC complexes have the steric and electronic attributes to be highly effective in generating allenes, paving the way for the development of additional olefin metathesis reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(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)
Article
Polymer Science
Yingying Zheng, Han Zhu, Xianchen Huang, Yixian Wu
Summary: The study demonstrates the successful synthesis of living cis-polybutadiene chains with desired molecular weights through polymerization process or sequential addition of an extra monomer, leading to the formation of amphiphilic silicon hydroxyl-functionalized cis-PB. Star-shaped cis-PBs are formed through self-assembly via hydrogen bonding from -Si(OH)3 groups, with surface transformation from hydrophobic to hydrophilic observed after water induction in lower molecular weight cis-PB segments. The hydrophilic cis-PB-Si(OH)3 films show good self-healing behavior, suggesting potential applications in recyclable elastomers and self-healing elastic coatings with low-temperature resistance.
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, Physical
Antonio Del Vecchio, Jakub Talcik, Sophie Colombel-Rouen, Jan Lorkowski, Melinda R. Serrato, Thierry Roisnel, Nicolas Vanthuyne, Guy Bertrand, Rodolphe Jazzar, Marc Mauduit
Summary: New Blechert-type ruthenium complexes with cyclic(alkyl)(amino)carbene (CAAC) ligands show remarkable thermal stability in solution and excellent catalytic performances in various metathesis reactions. They exhibit high catalytic activity at low loading and can achieve high enantiomeric excess in asymmetric metathesis reactions.
Article
Polymer Science
Alessandra Travanut, Patricia F. Monteiro, Stefan Oelmann, Steven M. Howdle, Anna M. Grabowska, Philip A. Clarke, Alison A. Ritchie, Michael A. R. Meier, Cameron Alexander
Summary: The Passerini three component reaction (Passerini-3CR) is utilized to synthesize an amphiphilic diblock copolymer for drug delivery applications. The versatility of Passerini-3CR allows for customization through post-functionalization, demonstrating potential clinical utility.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Article
Polymer Science
Luca Filippi, Michael A. R. Meier
Summary: This work presents a straightforward and efficient synthesis approach for renewable non-isocyanate polyurethanes (NIPUs) by synthesizing suitable carbamate monomers and sustainable dithiols, followed by polymerization using the thiol-ene reaction. The obtained polymers were characterized by various analytical techniques to confirm their properties and structure.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Article
Polymer Science
Kevin A. Waibel, Dafni Moatsou, Michael A. R. Meier
Summary: Linear uniform oligomers are modified with octaethylene glycol monomethyl ether and coupled via azide-alkyne cycloaddition to form uniform star-shaped block macromolecules with a mass ranging from 10 to 14 kDa. Characterized by NMR, ESI-MS, and SEC, these macromolecules are then tested for their ability to encapsulate dye molecules in qualitative solid-liquid phase transfer experiments.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Article
Polymer Science
Julian T. Windbiel, Michael A. R. Meier
Summary: The Biginelli reaction was utilized to synthesize a set of 15 new fully renewable poly(3,4-dihydropyrimidin-2(1H)-one)s through a simple one-pot multicomponent approach, showing high glass transition temperatures and good thermal stability.
POLYMER INTERNATIONAL
(2021)
Article
Materials Science, Paper & Wood
Mina Heidari, Kelechukwu N. Onwukamike, Etienne Grau, Stephane Grelier, Henri Cramail, Michael A. R. Meier, Andreas Greiner
Summary: The study utilized the DBU-CO2 switchable solvent system for the direct electrospinning of cellulose, showing promising results. Different cellulose types and combinations with PVA were investigated to achieve unique fiber structures. Challenges in solvent removal and exploration of coagulation collection process for fiber recovery were highlighted.
Article
Chemistry, Organic
Kevin A. Waibel, Dennis Barther, Triantafillia Malliaridou, Dafni Moatsou, Michael A. R. Meier
Summary: An efficient isocyanide-based synthesis of S-thiocarbamates was developed, allowing direct conversion of N-formamides into thiocarbamates without the need for isolation and purification of the isocyanide component, thus reducing environmental impact and increasing synthesis efficiency. The method was applied to synthesize a library of sixteen thiocarbamates and investigate reaction mechanism, as well as preparing four norbornene-based thiocarbamate monomers for controlled ring-opening metathesis polymerization (ROMP) reactions. The resulting polymers were characterized using size-exclusion chromatography (SEC) and their properties were analyzed with differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yasmin S. Raupp, Pia S. Loeser, Silke Behrens, Michael A. R. Meier
Summary: The study found that palladium nanoparticles, stabilized by poly(vinylpyrrolidone), catalyze the ring-opening of limonene dioxide with water, showing selectivity. Different concentrations of poly(vinylpyrrolidone) alone resulted in different selectivities towards exo-cyclic or endo-cyclic epoxide ring-opening.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2021)
Article
Chemistry, Multidisciplinary
Jonas Wolfs, Roman Nickisch, Lisa Wanner, Michael A. R. Meier
Summary: The study introduces a novel concept combining tandem catalysis and cellulose derivatization, utilizing a single catalyst for three transformations in a DMSO/DBU/CO2 switchable solvent system. Results show that the tandem reaction approach is more beneficial in terms of efficiency and sustainability compared to stepwise synthesis. By analyzing the obtained products, researchers controlled the degree of substitution of O-cellulose thiocarbamates.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Polymer Science
Julian T. Windbiel, Michael A. R. Meier
Summary: The research focuses on the synthesis of a renewable methacrylate monomer based on ricinoleic acid, which can be used in radical polymerization techniques like RAFT. Post-polymerization modification using the B-3CR allows for the synthesis of polymers with increased glass transition temperature.
MACROMOLECULAR CHEMISTRY AND PHYSICS
(2022)
Editorial Material
Chemistry, Multidisciplinary
Belen Martin-Matute, Michael A. R. Meier, Thomas-Xavier Metro, Stefan G. Koenig, Helen F. Sneddon, Putla Sudarsanam, Paul Watts
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2021)
Editorial Material
Chemistry, Multidisciplinary
David T. Allen, D. Julie Carrier, Jingwen Chen, Nicholas Gathergood, Jeannette M. Garcia, Jinlong Gong, Hongxian Han, King Kuok (Mimi) Hii, Bing-Joe Hwang, Asha Liza James, Mihir Jha, Peter Licence, Andrew C. Marr, Michael Meier, Audrey Moores, Ryuhei Nakamura, Thalappil Pradeep, Liane Rossi, Bert Sels, Bala Subramaniam, Michael K. C. Tam, Lin Zhuang, Julio F. Serrano
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2021)
Article
Polymer Science
Anja Kirchberg, Masood Khabazian Esfahani, Marie-Christin Roepert, Manfred Wilhelm, Michael A. R. Meier
Summary: This work demonstrates the synthesis of non-isocyanate poly(ester urethane)s in a sustainable manner by obtaining cyclic carbonates from renewable diols and reacting them with renewable 11-amino undecanoic acid methyl ester. Various purification strategies are compared and alternative starting materials are explored. The synthesized materials are fully characterized and their rheological properties are investigated.
MACROMOLECULAR CHEMISTRY AND PHYSICS
(2022)
Article
Polymer Science
Roman Nickisch, Peter Conen, Michael A. R. Meier
Summary: This study presents an easy access to thermoplastic polythiosemicarbazones (polyTSCs) through condensation reaction, resulting in a variety of polymers and copolymers that were thoroughly characterized. The polymerization proceeds at room temperature with broad moiety tolerance, and the synthesized polymers exhibit good thermal stability.
Article
Materials Science, Biomaterials
Alessandra Travanut, Patricia F. Monteiro, Sean Smith, Steven M. Howdle, Anna M. Grabowska, Barrie Kellam, Michael A. R. Meier, Cameron Alexander
Summary: Passerini reactions are suitable for the preparation of drug delivery materials, enabling efficient drug conjugation and encapsulation, as well as enhanced efficacy against TNBC cells.
JOURNAL OF MATERIALS CHEMISTRY B
(2022)
Article
Chemistry, Multidisciplinary
Jonas Wolfs, Michael A. R. Meier
Summary: The homogeneous cellulose acetylation process using the DBU/CO2 switchable solvent system is demonstrated to be efficient and sustainable, utilizing vinyl acetate as a benign acetylation agent under mild conditions. It allows for straightforward recyclability of all components with high recycling ratios (87.0-98.9%). Compared to traditional methods, this process shows less cellulose backbone degradation and improved mechanical properties of solvent casted foils, resulting in an E-factor of 1.92 for the overall process, emphasizing sustainability and efficiency.
