Article
Chemistry, Physical
Roushan Prakash Singh, Soumen Sinhababu, Neal P. Mankad
Summary: This Perspective reviews recent advances and applications of Al/M heterobimetallic catalysis in various areas, including polymerization, epoxide activation and carbonylation. The mechanistic role of the aluminum site is highlighted, and a comprehensive perspective is constructed by including a broad range of Al-containing metalloligands and Al/M combinations.
Article
Chemistry, Multidisciplinary
Tiziana Fuoco
Summary: The clever combination of ring-opening polymerization (ROP) and step-growth polymerization (SGP) allows for the design of a library of sequence-controlled polymers with diverse degradability functions. This strategy offers higher chemical diversity and control over primary structure, while being simple, effective, and atom-economical.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Louise Ponsard, Emmanuel Nicolas, Ngoc Huan Tran, Sarah Lamaison, David Wakerley, Thibault Cantat, Marc Fontecave
Summary: A system coupling high-pressure CO2 electrolysis with thermal catalysis using high-pressure CO has been developed to convert CO2 into beta-butyrolactone, achieving a high reaction yield. This strategy enables the production of lactones from CO2 for polyester synthesis, expanding the range of chemicals derived from CO2.
Article
Chemistry, Multidisciplinary
Jin-Chuang Yang, Jun Yang, Wen-Bing Li, Xiao-Bing Lu, Ye Liu
Summary: Polyhydroxyalkanoates (PHAs) are biodegradable polyesters with potential to replace petroleum-based plastics. Tri-metallic complexes were used for carbonylative polymerization, resulting in high-performance PHAs. This study provides a new method for synthesizing poly-β-lactones.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Frederic St-Jean, Remy Angelaud, Stephan Bachmann, Diane E. Carrera, Travis Remarchuk, Katarzyna A. Piechowicz, Katrin Niedermann, Hans Iding, Roland Meier, Haiyun Hou, Lauren E. Sirois, Jie Xu, Martin Olbrich, Pankaj Rege, Maud Guillemot-Plass, Francis Gosselin
Summary: A highly efficient asymmetric synthesis of the IDO inhibitor navoximod was described, featuring the stereoselective installation of two relative and two absolute stereocenters from an advanced racemic intermediate. The stereocenters were set via crystallization-induced dynamic resolution along with two selective ketone reductions. By following this strategy, navoximod was synthesized in 10 steps with high yield and purity.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Fanni Bede, Laszlo Kollar, Nandor Lambert, Peter Huszthy, Peter Pongracz
Summary: Palladium-catalyzed hydroaminocarbonylation reactions of olefins using aliphatic amines were successfully performed under carbon monoxide atmosphere. The targeted amides were synthesized in moderate to good isolated yields without the need for acidic additives. The effect of chiral diphosphines on product distribution, including chemo-, regio-, and enantioselectivities, was also investigated.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Physical
Xuehua Zhang, Yanwei Cao, Qiongyao Chen, Chaoren Shen, Lin He
Summary: Efficient chemical conversion of CO2 is crucial for reducing emissions and creating economic value, with homogeneous reductive carbonylation being a promising approach.
ACTA PHYSICO-CHIMICA SINICA
(2021)
Article
Chemistry, Physical
Beata Gatlik, Wojciech Chaladaj
Summary: A Pd-catalyzed three-component protocol was developed for the direct synthesis of perfluoroalkyl-substituted alpha,beta-unsaturated esters using formates as convenient CO sources. The reaction proceeded smoothly under mild conditions with high yields and excellent selectivities. Detailed mechanistic studies supported by DFT calculations were conducted to understand the reaction pathway.
Article
Chemistry, Physical
Huaifeng Li, Daniel Lupp, Pradip K. Das, Li Yang, Theo P. Goncalves, Mei-Hui Huang, Marwa El Hajoui, Lan-Chang Liang, Kuo-Wei Huang
Summary: The new imination methodology with a base-metal nickel PN3 pincer catalyst features one-step, waste-free, and high atom-economical characteristics, avoiding the difficulties in purification and waste disposal in traditional methods. Mechanistic insight reveals a non-metal-ligand cooperation pathway, providing an important theoretical basis for modern organic synthesis.
Article
Chemistry, Multidisciplinary
Taichi Kusakabe, Dongwei Liu, Kaori Tsuchida, Shun Okazaki, Tsuyoshi Hashimoto, Akane Mori, Kentaro Yoshiwaka, Hiroaki Sasai, Keisuke Takahashi, Keisuke Kato
Summary: The palladium-catalyzed methoxy-methoxycarbonylation of monosubstituted allenes was reexamined. It was found that arylallenes provided methyl 2-methoxymethylacrylates in good yield with moderate to good enantioselectivity, while alkylallenes afforded methyl 2-methoxymethylacrylates regioselectively but with low enantioselectivity.
Review
Chemistry, Multidisciplinary
Kanokon Upitak, Christophe M. Thomas
Summary: Almost all aspects of daily life involve polymers in some form or the other. However, polymer production is largely based on finite feedstocks. The conversion of biomass into resources suitable for polymer production is a crucial challenge for a more sustainable chemical economy. Catalysis plays an important role in supporting more sustainable plastics production. One-pot catalysis represents an exciting frontier in materials science, enabling the synthesis of sustainable materials for a wide range of applications and reducing the environmental footprint.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Review
Chemistry, Physical
Tommaso Lorenzetto, Fabrizio Fabris, Alessandro Scarso
Summary: In the field of green chemistry, micellar catalysis is important for replacing organic solvents. Micelles ensure the solubilization or dispersion of catalyst and organic substrates in water, providing unique features in terms of chemo-, regio-, and stereoselectivity. Metallosurfactants, which are hydrophilic metal-containing headgroups endowed with a hydrophobic ponytail, offer a more robust approach for catalyst recycling in metal-catalyzed reactions. This review critically examines the research progress since 2017, discussing new trends and classifying the literature based on the nature of the newly formed bond. The specific features of metallosurfactants in terms of activities, selectivities, and recyclability of self-assembling catalysts are emphasized.
CURRENT OPINION IN COLLOID & INTERFACE SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Laurynas Gausas, Bjarke S. Donslund, Steffan K. Kristensen, Troels Skrydstrup
Summary: Polyurethane (PU) is a commonly used thermoset plastic with complex structure, leading to challenges in recycling. The study shows that catalytic hydrogenation of PU materials using a manganese catalyst can effectively deconstruct PU into original monomer components for efficient recovery.
Review
Chemistry, Multidisciplinary
Yutan D. Y. L. Getzler, Robert T. Mathers
Summary: This paper discusses the evolution of environmentally responsible research in polymer chemistry and proposes solutions for achieving sustainability. The authors provide a historical overview and trace their own responses and research projects. They suggest moving beyond qualitative use of the 12 Principles of Green Chemistry and adopting a portfolio of metrics. The authors also propose the creation of a national Life Cycle Assessment center.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Physical
Qiankun Li, Chaoqun Wang, Hongliang Mu, Zhongbao Jian
Summary: This study presents a catalyst derived from cheap materials and short synthetic pathways that exhibits superior catalytic properties in olefin polymerization, enabling the formation of high molecular weight polyethylene.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Fei Lin, Stefan Mecking
Summary: In this study, water-soluble synthetic transition metal catalysts were synthesized for olefin polymerization. The nickel catalysts with hydrophilic active sites demonstrated high activity and produced high molecular weight polyethylene in aqueous conditions, even at elevated temperatures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Polymer Science
Benjamin A. Paren, Manuel Haeussler, Patrick Rathenow, Stefan Mecking, Karen Winey
Summary: We have presented a set of sulfonated monodisperse telechelic polyethylene ionomers that demonstrate ion transport of metal cations in layered ionic assemblies. These polymers have well-defined structures and exhibit different crystal packing and ion transport properties at different temperatures.
Article
Chemistry, Multidisciplinary
Jinseok Park, Anne Staiger, Stefan Mecking, Karen I. Winey
Summary: This study demonstrates that ionic functionality in a multiblock architecture can produce highly ordered nanostructures in thin films, including bicontinuous double gyroids. The researchers propose a versatile pathway to fabricating ordered nanostructures in thin films using ion-functionalized multiblock copolymers.
ACS CENTRAL SCIENCE
(2022)
Article
Chemistry, Multidisciplinary
Lukas Odenwald, Florian P. Wimmer, Nina K. Mast, Max G. Schussmann, Manfred Wilhelm, Stefan Mecking
Summary: Vitrimers combine the advantages of cross-linked materials with thermoplastic processability. Functionalized polyethylenes with cross-linkable groups were directly generated by catalytic insertion polymerization. These vitrimers exhibit excellent material properties and can be recycled due to reversible cross-linking.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Maria Voccia, Lukas Odenwald, Maximilian Baur, Fei Lin, Laura Falivene, Stefan Mecking, Lucia Caporaso
Summary: Polyethylene materials with in-chain-incorporated keto groups can be achieved by nonalternating copolymerization of ethylene with carbon monoxide using Ni(II) phosphinephenolate catalysts. The mechanism of this reaction involves the isomerization of an alkyl-olefin intermediate as the rate-determining step. The formation of non-alternating incorporation is influenced by ethylene binding, while the formation of alternating motifs is determined by the opening of the C,O-chelate. The crucial feature of these Ni(II) catalysts is the eta(2)-coordination of a P-bound aromatic moiety axially oriented to the metal center, which also affects the competition between the two pathways. The conformational constraints imposed in a 2',6'-dimethoxybiphenyl moiety result in disfavoring ethylene coordination along the alternating incorporation pathway, primarily governed by electronics, while not penalizing the nonalternating chain growth, primarily governed by sterics.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Amelie Fuchs, Stefan Mecking
Summary: This study reports an organometallic-mediated radical copolymerization method for carbon monoxide and ethylene, leading to the synthesis of keto-modified polyethylenes. The presence of carbon monoxide enhances the controlled character of the copolymerization by suppressing unfavorable termination pathways.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Polymer Science
Jinseok Park, Anne Staiger, Stefan Mecking, Karen Winey
Summary: Enhanced Li+ transport is demonstrated through selectively solvated ionic layers of a single-ion conducting polymer. The solvation of ionic domains with dimethyl sulfoxide (DMSO) accelerates structural relaxation and dissociation of ion pairs, leading to a significant enhancement of ion transport.
Article
Chemistry, Multidisciplinary
Marcel Eck, Simon Timm Schwab, Taylor Frederick Nelson, Katrin Wurst, Steffen Iberl, David Schleheck, Christoph Link, Glauco Battagliarin, Stefan Mecking
Summary: We have developed a new polyester material using biobased 1,18-octadecanedicarboxylic acid and ethylene glycol, which has a solid-state structure similar to polyethylene and comparable tensile properties to high density polyethylene (HDPE). Despite its crystallinity, high melting point and hydrophobic nature, the polyester-2,18 can be rapidly and completely hydrolytically degraded in vitro by naturally occurring enzymes. It also shows high biodegradability under industrial composting conditions and can be depolymerized by methanolysis for closed-loop recycling.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Stefanie de Roo, Felix Einsiedler, Stefan Mecking
Summary: This study demonstrates the catalytic conversion of renewable plant oils, including microalgae and waste oil, into industrially relevant alpha-olefins in the C-3 to C-10 regime. The biorefinery concept involves a catalytic sequence of ethenolysis, double bond isomerization, and subsequent ethenolysis, effectively rearranging the fatty acid chains into valuable chemical building blocks. Supercritical carbon dioxide (scCO(2)), a benign extraction and reaction solvent, is utilized.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Marcel Eck, Lea Bernabeu, Stefan Mecking
Summary: Researchers have developed a method to make PE-18,18 hydrolytically degradable by blending it with long-chain aliphatic poly(H-phosphonate)s. The blends exhibited similar properties to HDPE and showed complete hydrolysis of the poly(H-phosphonate)s component within four months under aqueous conditions. This hydrolysis led to embrittlement and fragmentation of the specimens, promoting eventual mineralization in the environment.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Maximilian Baur, Nina K. Mast, Jan P. Brahm, Rosa Habe, Tobias O. Morgen, Stefan Mecking
Summary: In this study, we modified polyethylene using both ketone and ester functional groups, and found that the simultaneous presence of both groups has no adverse effects on the crystal structure and thermal properties of polyethylene. Through oxidation of the in-chain ketone groups, high molecular weight polyethylenes with in-chain ketone-ester groups can be synthesized, which exhibit good photolytic degradation and chemical recyclability. We also demonstrated that polyethylenes bearing in-chain ketone groups can be produced via post-polymerization Baeyer-Villiger oxidation, combining the photodegradability of ketones with the chemical access point of esters.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Taylor F. Nelson, Dario Rothauer, Michael Sander, Stefan Mecking
Summary: Monomers sourced from waste or biomass, such as polyethylene waste or bio-based fatty acids, can be used to synthesize polyesters with various chain lengths. These polyesters exhibit high-density polyethylene-like properties, are ductile, and can be processed into films and fibers. They also show potential for chemical recycling or biodegradation in the environment.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Frieder Conradt, Vincent Bezold, Volker Wiechert, Steffen Huber, Stefan Mecking, Alfred Leitenstorfer, Ron Tenne
Summary: This study demonstrates the causal link between the quantum-confined Stark effect and spectral diffusion, and reveals the relation between the sensitivity of transition energy to an electric field and amplified spectral fluctuations. This is important for overcoming the critical barrier in applications of quantum sensing.
Article
Polymer Science
Stephanie F. Marxsen, Manuel Haeussler, Marcel Eck, Stefan Mecking, Rufina G. Alamo
Summary: In this study, the isothermal overall crystallization rates and linear growth rates of four symmetric long-spaced aliphatic polyesters were investigated. It was found that the polyesters exhibited discrete rate minima with increasing crystallization temperature, and the number and depth of these minima depended on the length of the methylene spacer between esters. The occurrence of rate minima could be explained by the self-poisoning feature and the difference in crystal thickness between non-integer and integer layered crystals.
Article
Chemistry, Multidisciplinary
Anne Saumer, Stefan Mecking
Summary: We report the synthesis and properties of ion-containing, long-chain aliphatic polyesters that can be degraded and fully recycled. These polyesters exhibit desirable traits, such as adhesion with polar compounds, due to the presence of ionic groups. The mechanical properties and melt rheology of these polyesters are significantly influenced by the nature of the cation counterions. Additionally, these polyesters can be chemically recycled by depolymerization. Our findings provide opportunities for tuning the properties of recyclable polyethylene-like polymers.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)