Article
Chemistry, Multidisciplinary
Yuki Saito, Shu Kobayashi
Summary: The application of heterogeneous catalysts in continuous-flow enantioselective hydroacylation reactions was studied. Catalysts were prepared by mixing supports and rhodium complexes, and showed excellent activity and enantioselectivity. Under optimized conditions, the catalysts exhibited high turnover numbers and could be applied to various substrates. Furthermore, sequential-flow reactions with other heterogeneous catalysts were demonstrated for the synthesis of biologically active molecules and functional materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Lixian Wang, Jin Lin, Qiangsheng Sun, Chungu Xia, Wei Sun
Summary: A series of Mn(I) catalysts with chiral bidentate benzimidazoles derived from easily available amino acids have been developed for asymmetric transfer hydrogenation (ATH), showing high activity and enantioselectivity. These phosphine-free chiral Mn catalysts can efficiently convert bulky substrates into drug intermediate alcohols, with a possible mechanism and enantiocontrol model proposed based on experimental and DFT studies.
Article
Chemistry, Organic
Bin Li, Jiaxin Wang, Xiaoye Li, Jiayue Xi, Ruoxuan Wang, Dongxu Zhang, Xiaohui Zheng, Huifang Nie, Shengyong Zhang
Summary: An efficient enantioselective hydrogenation method was described for the preparation of chiral cyclic amines, which are useful for natural product modification and drug molecular preparation. High yields and moderate to excellent enantioselectivities were achieved, making this method valuable for synthesis applications.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Masa Sterle, Matej Hus, Matic Lozinsek, Anamarija Zega, Andrej Emanuel Cotman
Summary: Stereopure CF3-substituted syn-1,2-diols were synthesized through the reductive dynamic kinetic resolution of corresponding alkyl ketones, yielding products with >95% ee and >87:13 syn/anti ratio. This method provides a rapid access to stereopure bioactive molecules. Moreover, DFT calculations were conducted on three types of Noyori-Ikariya ruthenium catalysts to demonstrate their general ability to control stereoselectivity through hydrogen bond acceptor SO2 region and CH/pi interactions.
Article
Chemistry, Physical
Zhengyu Han, Gang Liu, Xuanliang Yang, Xiu-Qin Dong, Xumu Zhang
Summary: The study developed an efficient and simple synthetic strategy for obtaining both enantiomers of chiral tetrahydroquinoline derivatives through the adjustment of reaction solvents. Gram-scale asymmetric hydrogenation proceeded well with low-catalyst loading, and a possible reaction process was revealed based on various experiments conducted.
Article
Chemistry, Inorganic & Nuclear
Kristina Zivkovic, Lilia M. Baldauf, Jessica L. Cryder, Alexa Villasenor, Valeria Reyes, Lauren E. Bernier, Theresa J. Thomas, Maxwell O'Toole, Kayleen Fulton, Curtis E. Moore, Arnold L. Rheingold, Christopher J. A. Daley
Summary: The study reports the first isolation and structural characterization of a series of chiral trinitrogen pincer ligands, as well as the methods for their preparation. Experimental results show that a novel microwave-based technique is more efficient, although currently not scalable.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Sopon Butcha, Veronique Lapeyre, Chularat Wattanakit, Alexander Kuhn
Summary: In modern chemistry, chiral (electro)catalysis is a crucial strategy for producing enantiomerically pure compounds. However, uncontrollable stereochemistry due to side reactions remains a challenge for chiral catalysis. This study proposes a synergetic combination of two strategies: the design of mesoporous Pt films with chiral recognition sites, and the controlled formation of a self-assembled monolayer. By selectively functionalizing the electrode's surface with a monolayer of organosulfur ligands, undesired side reactions are significantly suppressed, leading to an increase in enantiomeric excess to over 90% in the context of enantioselective electrosynthesis. This strategy also greatly reduces the total reaction time. Overall, this study opens up promising possibilities for the development of heterogeneous enantioselective electrocatalysis strategies.
Article
Chemistry, Organic
Lucas Bacheley, Ricardo Molina Betancourt, Rathies Ravindra, Gerard Guillamot, Phannarath Phansavath, Virginie Ratovelomanana-Vidal
Summary: A straightforward method for synthesizing novel families of enantioenriched cis-monofluorinated carbocyclic alcohols has been developed using ATH/DKR. The reaction exhibited high yields (up to 97%), high diastereoselectivity (up to 99:1 dr), and high enantioselectivity (up to 97% ee). Additionally, trans-difluorinated indans, tetrahydronaphthalenes, tetrahydroquinolines, and chromans were synthesized via deoxofluorination of the corresponding cis-fluoro alcohols.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Nan Ji, Qinqin Tian, Qingqing Yang, Minghua Li, Wei He
Summary: This study describes a highly enantioselective epoxidation of trans-alpha-cyano-alpha, beta-unsaturated esters using cinchona alkaloid-derived urea and H2O2 as organocatalysts and oxidant, resulting in chiral glycidic ester derivatives with cyano groups in good yields (up to 95%) and excellent enantioselectivities (up to 97% ee). A plausible transition state was proposed for the reaction mechanism.
TETRAHEDRON LETTERS
(2021)
Review
Chemistry, Organic
Koji Hirano
Summary: This review focuses on the importance of organofluorine compounds in pharmaceuticals and agrochemicals, with particular emphasis on the challenges and recent advances in the catalytic enantioselective synthesis of sp(3) carbon-based alkyl-CF3-containing molecules.
SYNTHESIS-STUTTGART
(2022)
Review
Chemistry, Organic
Dezheng Xie, Ziyi Chen, Chun-Jiang Wang, Xiu-Qin Dong
Summary: Phosphonates and derivatives with an α-chiral center are important compounds found in natural products, pharmaceuticals, and agrochemicals. The synthesis of these compounds has been the focus of recent research, with advancements in asymmetric catalysis such as hydrogenation, addition reactions, and nucleophilic additions to α,β-unsaturated phosphonates. The continuous development of enantioselective catalytic methods and the future applications of these compounds are also discussed.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Physical
Jose A. Carmona, Carlos Rodriguez-Franco, Joaquin Lopez-Serrano, Abel Ros, Javier Iglesias-Siguenza, Rosario Fernandez, Jose M. Lassaletta, Valentin Hornillos
Summary: An efficient dynamic kinetic resolution (DKR) approach has been developed for the synthesis of axially chiral diamines based on ruthenium-catalyzed enantioselective transfer hydrogenation. This method features a broad substrate scope and proceeds under very mild conditions, allowing the preparation of BINAM homologues in good to high yields and nearly perfect enantioselectivities (up to 99% ee).
Editorial Material
Chemistry, Multidisciplinary
Bing Fang, Yixuan Li, Fazheng Ren
Summary: In a recent Nature paper, Xu et al. reported the synthesis of chiral Au nanoparticles with the highest g-factor value. These chiral nanoparticles can regulate immune cell maturation, opening up the possibility of using nano scale chirality as an adjuvant for vaccines.
Review
Chemistry, Organic
Adam Mark Palvolgyi, Fabian Scharinger, Michael Schnuerch, Katharina Bica-Schroeder
Summary: Chiral phosphoric acid catalysts show high activity and enantioselectivity in organocatalytic asymmetric transfer hydrogenation, with promising development prospects. These catalysts are widely used in asymmetric reduction reactions of various compounds, and are increasingly applied in multicomponent/cascade reactions, demonstrating significant synthetic potential.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Xu Chen, Zhiwei Qiao, Bang Hou, Hong Jiang, Wei Gong, Jinqiao Dong, Hai-Yang Li, Yong Cui, Yan Liu
Summary: Metal-organic frameworks (MOFs) have shown great potential in heterogeneous catalysis, and the enantioselectivities of chiral MOF (CMOF) catalysts can be significantly enhanced by designing metals and ligands, resulting in improved chiral catalytic reactions.
Article
Chemistry, Physical
Xianwei Wang, Nobutaka Maeda, Daniel M. Meier, Alfons Baiker
Summary: The catalytic reduction of NO with CO was studied over monometallic Au and bimetallic AuRh nanoparticles supported on potassium titanate (KTN) and TiO2, with KTN showing significant enhancement in catalytic performance. The support material plays a crucial role in promoting the formation of surface species, particularly isocyanide, which is important for producing dinitrogen molecules via reaction with NO.
Article
Nanoscience & Nanotechnology
Song Guo, Guomei Zhang, Zhong-Kang Han, Shaoyang Zhang, Debalaya Sarker, Wen Wu Xu, Xiaoli Pan, Gao Li, Alfons Baiker
Summary: The ternary PdO-CeO2-OMS-2 catalyst shows excellent performance in selectively reducing NO and CO, converting them nearly completely to N-2. Analysis of the catalyst's structural and chemical properties reveals the crucial role of lattice oxygen vacancies and oxygen diffusion in this multicenter reaction system.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Physical
Ammara Waheed, Xianwei Wang, Nobutaka Maeda, Daniel M. Meier, Tamao Ishida, Toru Murayama, Masatake Haruta, Alfons Baiker
Summary: The study found that the formation of bidentate ethoxy species and adsorption of ethanol are key factors for high activity and selectivity in the gold-catalyzed oxidation of ethanol to acetic acid. Co3O4 was identified as the best support material to meet these requirements, while monodentate ethoxy species on NiO deteriorated the catalytic performance.
CATALYSIS COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Xianwei Wang, Nobutaka Maeda, Daniel M. Meier, Alfons Baiker
Summary: The nanocomposite consisting of bimetallic AuPd nanoparticles modified with CeO2 and deposited on potassium titanate nanobelts exhibited outstanding catalytic performance in the selective catalytic reduction of NO with CO. The favorable synergies between the components led to full NO conversion and high selectivity to N-2. The alloying of Au with Pd enhanced the ability to adsorb CO and NO on the surface, contributing to the high conversion and selectivity.
Review
Chemistry, Multidisciplinary
Antonio J. Martin, Cecilia Mondelli, Shibashish D. Jaydev, Javier Perez-Ramirez
Summary: This article discusses the importance of chemocatalytic transformations in addressing plastic pollution, providing a comprehensive analysis of the basic principles and applications of catalytic transformations of various plastics, and presenting relevant leading route systems. It emphasizes the role of the latest systems in the development field in driving material design to accelerate the development of a sustainable plastic economy.
Article
Chemistry, Physical
Basile Lasne, Paivi Maki-Arvela, Atte Aho, Zuzana Vajglova, Kari Eranen, Narendra Kumar, Julian E. Sanchez-Velandia, Markus Peurla, Cecilia Mondelli, Javier Perez-Ramirez, Dmitry Yu Murzin
Summary: In this study, various heterogeneous micro- and mesoporous, acidic catalysts were examined for the selective synthesis of Florol (R). The results showed that a mildly acidic, microporous H-Beta-300 catalyst with a SiO2/Al2O3 ratio of 300 performed the best, achieving 72% selectivity and 99% conversion at 40 degrees C with a molar ratio of isoprenol to isovaleraldehyde of 1:5. More acidic zeolite catalysts exhibited slightly lower selectivity, while mesoporous catalysts with mild acidity and no strong Bronsted acid sites had the lowest selectivity.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Physical
Zichun Wang, Yijiao Jiang, Alfons Baiker, Michael Hunger, Jun Huang
Summary: This study found that flame-derived amorphous silica-aluminas exhibit higher activity in hydrocarbon conversion reactions due to their enhanced surface acidity and local coordination environment. The flame-derived ASAs showed higher exchange rates and lower activation energy, attributed to the increased oxygen coordination with Al species, which enhances the ability to accept D+.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Physical
Thaylan Pinheiro Araujo, Jordi Morales-Vidal, Tangsheng Zou, Rodrigo Garcia-Muelas, Patrik O. Willi, Konstantin M. Engel, Olga V. Safonova, Dario Faust Akl, Frank Krumeich, Robert N. Grass, Cecilia Mondelli, Nuria Lopez, Javier Perez-Ramirez
Summary: This study investigates the effect of different metal promoters on the catalytic performance of In2O3 in CO2 hydrogenation to methanol. The results show that atomically-dispersed promoters exhibit the highest improvement in performance, while clustered and nanoparticle forms of metals have moderate or no promotion effect.
ADVANCED ENERGY MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Tangsheng Zou, Thaylan Pinheiro Araujo, Frank Krumeich, Cecilia Mondelli, Javier Perez-Ramirez
Summary: In this study, ZnO promotion on inverse ZrO2-Cu catalysts has been demonstrated to significantly enhance the catalytic activity for CO2-to-methanol conversion, with the underlying mechanism of ZnO's structural role and interaction with copper particles identified. The obtained high methanol space-time yield indicates the potential application value of this modification in sustainable production of key commodities and fuels.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Physical
Kyungho Lee, Uzma Anjum, Cecilia Mondelli, Qian He, Shinya Furukawa, Javier Perez-Ramirez, Sergey M. Kozlov, Ning Yan, Thaylan Pinheiro Arajo
Summary: In this study, an atomic Pd-promoted ZnZrOx solid solution catalyst (Pd-ZnZrOx) was designed and synthesized, showing excellent activity and stability in the conversion of CO2 to methanol.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2022)
Article
Chemistry, Physical
Yuhang Wang, Yifei Zhang, Qike Jiang, Song Guo, Alfons Baiker, Gao Li
Summary: The co-doping of ceria with Cu and Cr forming a ternary CuCrCeOx solid solution significantly improves the catalytic performance, N-2 selectivity, and NO/CO conversions. The coupling of different transition metal redox cycles and the surface population of oxygen vacancies contribute to the enhanced activity. The ternary CuCrCeOx catalyst exhibits the highest oxygen defect density and achieves 100% N-2 selectivity at lower temperatures.
Article
Multidisciplinary Sciences
Thaylan Pinheiro Araujo, Cecilia Mondelli, Mikhail Agrachev, Tangsheng Zou, Patrik O. Willi, Konstantin M. Engel, Robert N. Grass, Wendelin J. Stark, Olga Safonova, Gunnar Jeschke, Sharon Mitchell, Javier Perez-Ramirez
Summary: This study presents the synthesis of ternary Pd-In2O3-ZrO2 catalysts with remarkable methanol productivity and improved metal utilization using flame spray pyrolysis (FSP). Unlike traditional methods, the materials prepared by FSP combine low-nuclearity palladium species with highly dispersed In2O3 monolayers on the ZrO2 carrier. A pioneering protocol using in situ electron paramagnetic resonance spectroscopy reveals enhanced generation of oxygen vacancies in this unique catalyst architecture, explaining its high and sustained methanol productivity.
NATURE COMMUNICATIONS
(2022)
Review
Chemistry, Physical
Antonio J. Martin, Sharon Mitchell, Cecilia Mondelli, Shibashish Jaydev, Javier Perez-Ramirez
Summary: This article points out the overlooked issue of catalyst deactivation in catalysis research and proposes a unified classification of deactivation modes, which helps understand and mitigate catalyst deactivation.
Article
Chemistry, Physical
Konstanze R. Hahn, Alfons Baiker
Summary: The coadsorption of quinoline and hydrogen plays a crucial role in the hydrogenation of quinoline. This study used first-principles DFT simulations to investigate the coadsorption of quinoline and hydrogen on different metal surfaces. The adsorption modes of quinoline were found to vary on different metals, with pi-bonding on platinum group metals and sigma-bonding on gold. The adsorption strengths of quinoline also differed among the metals, with Rh, Pd, and Pt showing stronger adsorption than Au. The study also discussed the potential impacts of these adsorption behaviors on quinoline hydrogenation and the use of cinchonidine as a chiral modifier in enantioselective hydrogenation.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Multidisciplinary
Thaylan Pinheiro Araujo, Jordi Morales-Vidal, Georgios Giannakakis, Cecilia Mondelli, Henrik Eliasson, Rolf Erni, Joseph A. Stewart, Sharon Mitchell, Nuria Lopez, Javier Perez-Ramirez
Summary: Ternary Pd-In2O3/ZrO2 catalysts prepared by wet impregnation exhibit selective and stable architecture under CO2 hydrogenation conditions, irrespective of the order of addition of Pd and In phases on the zirconia carrier. The rapid restructuring of the catalysts is driven by the metal-metal oxide interaction energetics. The presence of InPdx alloy particles decorated by InOx layers prevents performance losses associated with Pd sintering.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
