Review
Chemistry, Multidisciplinary
Ting Yan, Heng Liu, Z. X. Zeng, W. G. Pan
Summary: This paper reviews the methods and catalysts for synthesizing cyclic carbonates using CO2 as the feedstock, and analyzes the mechanisms of CO2 activation and the suitability of different catalysts. This review provides timely insights into current research progress and offers valuable inspirations for future investigations on CO2-based cyclic carbonate synthesis.
JOURNAL OF CO2 UTILIZATION
(2023)
Article
Polymer Science
Ping Sen Choong, Yen Li Eunice Hui, Chen Chuan Lim
Summary: This study reports the synthesis of amine-CO2 adducts and their CO2 adsorption-desorption characteristics. The results show that the amine-CO2 adducts can exhibit up to 87% CO2 desorption at 60°C after aminolysis with cyclic carbonate. The amine-CO2 adduct is used as both a foaming agent and a comonomer to obtain low-density foams (0.203-0.239 g·cm(-3)) after heating at 50-60°C for 24-48h. This marks the successful synthesis of in situ CO2-blown NIPU foams using an amine-CO2 adduct.
Article
Materials Science, Multidisciplinary
Payal Tyagi, Devender Singh, Neeti Malik, Sumit Kumar, Rajender Singh Malik
Summary: Fossil fuels have contributed to prosperity and welfare, but their CO2 emissions have had a negative impact on global temperature. With limited fossil fuel resources, finding alternative carbon sources for a sustainable economy is necessary. The conversion of CO2 into cyclic carbonate through catalysts is discussed, with a focus on metal-catalyzed systems.
Article
Chemistry, Multidisciplinary
Giulia Chiarioni, Martin van Duin, Paolo P. Pescarmona
Summary: This study reports the fixation of carbon dioxide into novel rubber polymers based on polycarbonate domains. The researchers successfully synthesized polycarbonates with glass transition temperatures below room temperature and pendant double bonds along the backbone for cross-linking, resulting in an elastic rubber-like behavior. This opens up new possibilities for CO2-based green polycarbonates in various applications.
Article
Chemistry, Multidisciplinary
Cong Luo, Jiayi Wang, Houfang Lu, Kejing Wu, Yingying Liu, Yingming Zhu, Binshen Wang, Bin Liang
Summary: In this study, a one-pot synthesis of valuable glycerol carbonate (GC) from CO2, glycerol (Gly), and styrene oxide (SO) was successfully achieved using easily prepared protic ionic liquids (ILs) under atmospheric pressure. The high catalytic activity of 1,8-diazabicyclo[5.4.0]undec-7-enenium iodide (HDBUI) was attributed to the strong nucleophilicity and substrate activation provided by the synergistic effect of the protic HDBU+ cation and I- anion. High GC yields were also obtained when simulated flue gas and crude Gly were used as substrates.
Article
Chemistry, Organic
Changyue Ren, Anke Spannenberg, Thomas Werner
Summary: The synthesis of three bifunctional phosphonium salts with perfluorinated side chains is reported as catalysts for the synthesis of cyclic carbonates from epoxides and CO2. The most efficient catalyst with a phenolic substructure allows the synthesis of various carbonates at room temperature and low CO2 pressure. The use of perfluorodecalin improves yields and facilitates catalyst separation. However, the activity of recycled catalysts gradually decreases.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Zichen Ling, Qixin Zhou
Summary: This study explores the use of bio-based, low VOC and fast-curing waterborne NIPU for coating applications, with significant strides made in the coatings industry. The linseed oil-based cyclic carbonate was synthesized and used for the synthesis of waterborne non-isocyanate polyurethane coatings.
Article
Chemistry, Multidisciplinary
Yu Gu, Masazumi Tamura, Yoshinao Nakagawa, Kenji Nakao, Kimihito Suzuki, Keiichi Tomishige
Summary: In this study, the direct synthesis of polycarbonate diols from atmospheric pressure CO2 and alpha,omega-diols using a CeO2 catalyst in a flow reactor system was investigated. The efficient activation of CO2 and shifting of equilibrium towards the product were achieved through the removal of coproduced water. This method also showed high selectivity for the reactions of CO2 with primary mono-alcohols or 1,2-diols.
Article
Chemistry, Physical
Rui-Ying Zhang, Yue Zhang, Jian Tong, Lin Liu, Zheng-Bo Han
Summary: A bifunctional cationic covalent organic polymer was synthesized and investigated for its catalytic activity in the cycloaddition reaction of CO2 and epoxides. The aluminum in the polymer acts as a Lewis acid site, while the bromine ion acts as a nucleophile, leading to high conversion rates and stability in the reaction.
Article
Chemistry, Multidisciplinary
Haonan Lin, Cheng-Hua Deng, Xiaohang Qiu, Xiao Liu, Jian-Gong Ma, Peng Cheng
Summary: Three new manganese-based metal-organic frameworks have been synthesized with modified structures for improved catalytic activity in the reaction of CO2 and epoxides towards cyclic carbonates. The structures of the Mn-MOFs are controlled by changing the anions of the manganese salts, and the catalytic activities are optimized under mild conditions.
CRYSTAL GROWTH & DESIGN
(2021)
Article
Chemistry, Multidisciplinary
Saket Jain, Monojit Batabyal, Raviraj Ananda Thorat, Pratibha Choudhary, Raushan Kumar Jha, Sangit Kumar
Summary: Efficient synthesis of 2-phenyl-benzamide tellurenyl iodides was achieved by inserting a tellurium atom into the carbon-iodine bond of 2-iodobenzamides. These compounds were found to be effective catalysts for the activation of epoxide with CO2 for the synthesis of cyclic carbonates and the formation of 1,3-diaryl ureas from anilines and CO2. Mechanistic investigations revealed the formation of a catalytically active Te-N heterocycle intermediate.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Feng Han, Heng Li, Hongfeng Zhuang, Qin Hou, Qingfeng Yang, Bing Zhang, Chengxia Miao
Summary: The conversion of CO2 to high value-added chemicals is urgent due to the rise in carbon dioxide emissions and its importance as a renewable chlorine source. Developing efficient catalytic systems for the synthesis of cyclic carbonates is crucial for practical applications. The review article discusses the comprehensive developments in catalytic systems, classified into transition metal and transition-metal-free ones, with a focus on single- or multi-component catalytic systems. Transition-metal-free systems mainly involve quaternary ammonium salts or ionic liquids, while multi-component catalytic systems contain noble and nonnoble metals along with quaternary ammonium salts for catalysis. Insights from the intermediates in the mechanisms are presented for designing multifunctional catalysts and developing new transformation strategies.
JOURNAL OF CO2 UTILIZATION
(2021)
Article
Chemistry, Multidisciplinary
Sudiksha Aggrawal, Ruchi Sharma, Paritosh Mohanty
Summary: The study demonstrated that immobilizing CuO on paper matrices using an ultrafast microwave assisted method can achieve high yields in the conversion of CO2 and epoxides into cyclic carbonates. The synergy between the hydroxyl groups in the paper matrices and CuO is crucial for the formation of products.
JOURNAL OF CO2 UTILIZATION
(2021)
Article
Engineering, Chemical
Yi Yu, Xuan Feng, Zhuohang Xie, Ying Wu, Hongxia Xi
Summary: One-pot tandem synthesis of cyclic carbonates from olefins and CO2 is a promising strategy for CO2 fixation and high value chemical synthesis. However, the development of high performing catalysts with multifunctionalized catalytic sites in a single material remains a challenge. In this study, a Zr-BTB/PA-Co composite was successfully fabricated by combining dimension reduction and surface modification strategies. The composite exhibited increased Lewis base sites for enhanced CO2 adsorption and activation, as well as accessible intrinsic Lewis acid sites. This composite showed superior catalytic performance for the one-pot reaction of olefins and CO2 under mild conditions and even when using CO2 directly from air.
Article
Chemistry, Multidisciplinary
Zhifeng Xu, Wenting Wang, Bowei Chen, Haitao Zhou, Qiufang Yao, Xianjie Shen, Yuchen Pan, Dongxian Wu, Yongyong Cao, Zhangfeng Shen, Yanan Liu, Qineng Xia, Xi Li, Xiaoqin Zou, Yangang Wang, Lingchang Jiang
Summary: IL/ICOF composites were synthesized in situ via a one-pot route for catalytic cycloaddition of CO2 with epoxides. The prepared composites exhibit excellent CO2 adsorption capacity and catalytic performance, providing a new method for designing and constructing heterogeneous catalysts for CO2 capture and conversion.
CHEMICAL COMMUNICATIONS
(2023)
Article
Biochemistry & Molecular Biology
Aiga Grandane, Alessio Nocentini, Thomas Werner, Raivis Zalubovskis, Claudiu T. Supuran
BIOORGANIC & MEDICINAL CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Yuya Hu, Zhihong Wei, Anna Frey, Christoph Kubis, Chang-Yue Ren, Anke Spannenberg, Haijun Jiao, Thomas Werner
Summary: Hydroxy-functionalized phosphonium salts were studied as bifunctional catalysts for the conversion of CO2 with epoxides, with the phenol-based phosphonium iodide catalyst showing excellent efficiency. Under optimized conditions, the catalyst successfully converted epoxides to cyclic carbonates with high yields, demonstrating potential for pharmaceutical synthesis. DFT calculations rationalized the mechanism and efficiency of the phenol-based catalyst, highlighting the importance of hydrogen bonding in facilitating the ring-opening step.
Article
Chemistry, Applied
Xin Liu, Thomas Werner
Summary: The manganese catalyzed coupling of alcohols with phosphorus ylides was found to be controllable in terms of selectivity for forming carbon-carbon single and double bonds by adjusting ligands and reaction conditions. Compared to previous methods using precious metal complexes, this system utilizes earth abundant manganese catalysts, allowing for C-C and C=C bond formation in a sequential one-pot reaction. Mechanistic studies revealed that C-C bonds were generated through a borrowing hydrogen pathway, while C=C bond formation followed an acceptorless dehydrogenative coupling pathway.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Applied
Vivian Stefanow, Aiga Grandane, Marcus Eh, Johannes Panten, Anke Spannenberg, Thomas Werner
Summary: The natural compound (-)-alpha-cedrene has a weak woody and cedarlike odor, while the derivative cis-cedrene acetonide is a very powerful semisynthetic aroma molecule. The synthesis of cis-cedrene acetonide starting from cedrene can achieve an overall yield of <20%. Two synthetic pathways have been reported in this work, with the highest overall yield reaching 78%. An attempt to prepare the cis-diol with inverted stereochemistry was also made, resulting in the undesired trans-product in >99% yield.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2021)
Article
Chemistry, Organic
Linda Pudnika, Ilona Domraceva, Thomas Werner, Raivis Zalubovskis, Aiga Grandane
Summary: The study successfully synthesized compounds with potential biological activity containing benzoxepinone core structures through a simple and efficient synthetic route, and obtained diverse derivatives through late stage modification. This method is highly applicable for high throughput applications and provides a convenient pathway for further functionalization.
SYNTHESIS-STUTTGART
(2021)
Article
Environmental Sciences
Marisa A. Wirth, Lars Longwitz, Marion Kanwischer, Peter Gros, Peter Leinweber, Thomas Werner
Summary: Stable isotope labeling of pollutants is important for studying their environmental fate. A synthetic pathway to the labeled metabolite AMPA-N-15 was developed for the commonly used herbicide glyphosate, enabling its accurate detection and quantitation in soil extracts. The newly developed analysis concepts will facilitate future research on the environmental behavior of glyphosate.
ECOTOXICOLOGY AND ENVIRONMENTAL SAFETY
(2021)
Article
Chemistry, Organic
Changyue Ren, Anke Spannenberg, Thomas Werner
Summary: The synthesis of three bifunctional phosphonium salts with perfluorinated side chains is reported as catalysts for the synthesis of cyclic carbonates from epoxides and CO2. The most efficient catalyst with a phenolic substructure allows the synthesis of various carbonates at room temperature and low CO2 pressure. The use of perfluorodecalin improves yields and facilitates catalyst separation. However, the activity of recycled catalysts gradually decreases.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Constanza Terazzi, Karoline Laatz, Jan von Langermann, Thomas Werner
Summary: A simple catalytic system consisting of CaI2 and Et3N was used to efficiently cycloaddition of CO2 to a variety of epoxides, producing high yields of carbonates. The reaction mechanism involves the coordination of the amine to the Lewis acidic calcium center and the activation of the epoxide.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Physical
Constanza Terazzi, Anke Spannenberg, Jan von Langermann, Thomas Werner
Summary: The biocatalytic kinetic resolution of cyclic carbonates derived from glycerol was achieved using esterases and lipases. Pig Liver Esterase and Novozym (R) 435 showed the best selectivity, with E values of 38 and 49, respectively. The resolution of halogenated carbonates resulted in highly selective unconverted enantiomer, and Novozym (R) 435 showed good recyclability and stability.
Article
Plant Sciences
Pierre Yemback, Kenneth O. Eyong, Noella M. Efange, Michael HK. Kamdem, Derek T. Ndinteh, Patricia O. Odumosu, Gabriel N. Folefoc, Lawrence Ayong, Thomas Werner
Summary: Compounds from the Cameroon Natural Product Library (CANAPL) were screened against the enzyme target PfGAPDH to discover potential antimalarial agents. Lupeol cinnamate and oleanane cinnamate were identified as hits, and structurally similar triterpenoids from Baillonella toxisperma were isolated and screened. The optimized lupane derivatives showed potent antiplasmodial activities, with betulonic acid acryl aldehyde exhibiting the highest activity (IC50 = 0.703μM).
PHYTOCHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Changyue Ren, Constanza Terazzi, Thomas Werner
Summary: This paper reports an environmentally friendly organocatalytic N-formylation and N-methylation reaction of amines using CO2 as the C1 source and hydrosilanes as the reductant. By choosing different reductants and catalysts, selective conversion of substrates can be achieved, leading to the synthesis of a range of compounds.
Article
Chemistry, Physical
Constanza Terazzi, Anke Spannenberg, Jan von Langermann, Thomas Werner
Summary: The biocatalytic kinetic resolution of cyclic carbonates derived from glycerol was investigated in this study. A selection of enzymes was tested, and Pig Liver Esterase and Novozym (R) 435 showed the highest selectivity. The enzymes were successfully used for the conversion of 12 glycerol derivatives, and the resolution of halogenated carbonates exhibited excellent enantiomeric excess. Furthermore, Novozym (R) 435 showed good recyclability, retaining its activity after 10 cycles of reuse. The chiral carbonate obtained was further used for the synthesis of pharmaceutical compounds with high yield and enantiomeric ratio.
Article
Chemistry, Multidisciplinary
Xin Liu, Thomas Werner
Summary: A manganese pincer complex is reported as a versatile catalyst for the transfer hydrogenation of amides, carbamates, urea derivatives, and polyurethanes, leading to the corresponding alcohols, amines, and methanol. This method represents an approach to the indirect reduction of CO2 and shows the first examples of reduction of carbamates and urea derivatives as well as C-N bond cleavage in amides by transfer hydrogenation. The general applicability of this methodology is demonstrated by successful reduction of various compounds with good to excellent yields.
Article
Chemistry, Multidisciplinary
Jan Toenjes, Lars Longwitz, Thomas Werner
Summary: A catalytic, base-free Wittig reaction has been developed using PMHS as a terminal reductant, which allows for low catalyst loadings and compatibility with various functional groups. The system exhibits high stereoselectivity and yields up to 96%, making it a promising method for the synthesis of highly functionalized alkenes.
Article
Chemistry, Physical
Xin Liu, Lars Longwitz, Brian Spiegelberg, Jan Toenjes, Torsten Beweries, Thomas Werner
Article
Chemistry, Multidisciplinary
Xuemei Liu, Chaonan Cui, Shuoshuo Wei, Jinyu Han, Xinli Zhu, Qingfeng Ge, Hua Wang
Summary: This study presents a new strategy for designing efficient photocatalysts that can convert CO2 into hydrocarbons by utilizing synergistic catalytic sites. The findings provide a solution for the selective photocatalytic reduction of CO2 to CH4.
Article
Chemistry, Multidisciplinary
Chengxian Hu, Dan Wang, Lu Wang, Ying Fu, Zhengyin Du
Summary: A novel one-pot, three-component reaction conducted under electrochemical conditions was studied. The reaction involved 2-aminothiophenols, aldehydes, and malononitrile, using TBABF4 as an electrolyte and CuI as a catalyst. The proposed reaction mechanism suggested that CuI served as an electron relay. This method offers simplified operation, high atom economy, and mild reaction conditions.
Article
Chemistry, Multidisciplinary
Zhi Yang, Yu Chen, Linxi Wan, Yuxiao Li, Dan Chen, Jianlin Tao, Pei Tang, Fen-Er Chen
Summary: A highly enantioselective method for the complete hydrogenation of pyrimidinium salts using Ir/(S,S)-f-Binaphane complex as the catalyst was developed. This method provides easy access to fully saturated chiral hexahydropyrimidines, which are prevalent in many bioactive molecules. The reactions exhibit high yields and enantioselectivities under mild reaction conditions without additives. Successful application of this methodology in a continuous flow fashion further extends its practical utility.
Article
Chemistry, Multidisciplinary
Tina Jeoh, Jennifer Danger Nill, Wujun Zhao, Sankar Raju Narayanasamy, Liang Chen, Hoi-Ying N. Holman
Summary: In this study, the enzymatic hydrolysis of cellulose was investigated using real-time infrared spectromicroscopy. The spatial heterogeneity of cellulose was found to impact the hydrolysis kinetics. Hydration affected cellulose ordering, and Cel7A preferentially removed less extensively hydrogen bonded cellulose.
Article
Chemistry, Multidisciplinary
Tiphaine Richard, Walid Abdallah, Xavier Trivelli, Mathieu Sauthier, Clement Dumont
Summary: An effective method of grafting functionalities onto lignin based on glycerol carbonate has been developed using an efficient nickel-catalysed telomerisation reaction. This method allows lignin to have new reactive functions and reduces the glass transition temperatures of modified lignins, thereby expanding the application range of lignin-based resins.
Article
Chemistry, Multidisciplinary
Jing Qi, Xiyan Wang, Gan Wang, Srinivas Reddy Dubbaka, Patrick ONeill, Hwee Ting Ang, Jie Wu
Summary: This study presents a green and environmentally friendly approach for the synthesis of imides using electrocatalytic oxidation with H2O as the oxygen source. The method eliminates the need for toxic or expensive oxidants and achieves high yields under mild reaction conditions. It shows broad substrate compatibility and potential for industrial applications.
Article
Chemistry, Multidisciplinary
Babasaheb Sopan Gore, Lin-Wei Pan, Jun-Hao Lin, Yi-Chi Luo, Jeh-Jeng Wang
Summary: Here, we report a visible light-promoted intramolecular radical cascade reaction for the construction of fluorenol and naphthalene-fused cyclopropyl carbaldehyde derivatives. This method offers mild reaction conditions, a broad substrate scope, excellent step efficiency, and scalability, without the need for external chemical oxidants. The novelty of this protocol was demonstrated by synthesizing chrysene analogs and performing late-stage functionalizations.
Article
Chemistry, Multidisciplinary
Juho Antti Sirvio, Idamaria Romakkaniemi, Juha Ahola, Svitlana Filonenko, Juha P. Heiskanen, Ari Ammala
Summary: This article discusses the method of using supramolecular interaction between an aromatic hydrogen bond donor and lignin to achieve rapid delignification of softwood at low temperatures.
Article
Chemistry, Multidisciplinary
Yunyan Meng, Chunxiang Pan, Na Liu, Hongjiang Li, Zixiu Liu, Yao Deng, Zixiang Wei, Jianbin Xu, Baomin Fan
Summary: A novel visible light-driven synthesis method for 2,3-diamines has been developed, which has mild conditions, avoids the use of metal reagents, and can synthesize diamines and diols in one pot.
Article
Chemistry, Multidisciplinary
Mingqing Huang, Haiyang Huang, Mengyao You, Xinxin Zhang, Longgen Sun, Chao Chen, Zhichao Mei, Ruchun Yang, Qiang Xiao
Summary: A direct air-oxidized strategy for the synthesis of benzo[b]phosphole oxides was developed in this study. Arylphosphine oxides were transformed into phosphinoyl radicals, which were further combined with various alkynes to achieve the desired products. DFT calculations revealed the mechanism of phosphinoyl radical formation.
Article
Chemistry, Multidisciplinary
Anwei Wang, Jiayin Huang, Chunsheng Zhao, Yu Fan, Junfeng Qian, Qun Chen, Mingyang He, Weiyou Zhou
Summary: This study demonstrates an innovative strategy for the aerobic oxidation of C(sp(3))-H bonds using gamma-valerolactone. By optimizing the reaction conditions and utilizing specific catalysts, efficient oxidation of C(sp(3))-H bonds is achieved with good chemoselectivity in certain cases.
Article
Chemistry, Multidisciplinary
Shun Li, Likai Tong, Zhijian Peng, Bo Zhang, Xiuli Fu
Summary: Sulfide compounds show promise as electrocatalysts for water splitting, but their performance is limited by factors such as limited active sites and hindered substance transport. This study successfully prepared a high-entropy sulfide (ZnCoMnFeAlMg)(9)S-8, which reduced grain size and increased specific surface area, enabling the realization of a dual-functional catalyst with multiple catalytic sites. High entropy also modulated the electronic properties of sulfides, reducing the potential energy barrier for hydrolysis. This research introduces a new approach for functionalizing high entropy nanomaterials and improves the performance of water splitting catalysts.
