Article
Chemistry, Organic
Danielle L. J. Pinheiro, Martin Nielsen
Summary: The chemoselective reduction of enamides to alpha-amino acids using Ru pincer complexes as catalysts and iPrOH and EtOH as H-donors and solvents is demonstrated. A range of alpha-amino acids is synthesized with good to excellent yields. Applications, large-scale synthesis, and a one-pot experiment are also reported. Deuterium-labeling experiments show high regioselectivity between the alpha- and beta-positions of the alkene unit.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Zaneta Papadopulu, Martin Oestreich
Summary: A method for the nonenzymatic kinetic resolution of sterically congested alcohols with a quaternary carbon atom in the beta-position is reported, using the catalyst system CuCl/NaOtBu/(R,R)-Ph-BPE together with a 3,5-xylyl-substituted tertiary hydrosilane to achieve enantioselective silylation of the hydroxy group. Several alcohols are obtained with good to excellent selectivity factors, and there are currently no other known straightforward methods to access these motifs.
Article
Chemistry, Applied
Jiayu Zhou, Jianxun Ye, Yang Zhang, Zhaodi Li, Jingjing Li, Delong Liu, Wanbin Zhang
Summary: The RuPHOX-Ru catalyzed asymmetric hydrogenation of diaryl ketones has been developed, yielding chiral diaryl methanols with up to 99% yield and 99% ee. This protocol can be performed on a gram-scale with low catalyst loading (2000 S/C) and the resulting products are valuable for various transformations, especially in the synthesis of chiral drugs like (S)-Orphenadrine and (S)-Neobenodine. Deuterium labeling and control experiments revealed that the RuPHOX-Ru-catalyzed asymmetric hydrogenation is exclusively driven by H-2 as the hydrogen source.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Irena Dokli, Antonija Ozegovic, Aleksandra Simanovic, Matija Hromin, Anamarija Knezevic, Aleksandar Visnjevac, Andreja Lesac
Summary: Chiral liquid crystals (LCs) are promising functional soft materials with unique optical and mechanical properties. In this study, a versatile chiral 3-aryl-3-hydroxypropanoic ester moiety was introduced as a building block for LC compound preparation. Chiral LC compounds with diverse topologies were successfully synthesized, and their mesomorphic behavior was consistent with their topology. The study also identified different liquid crystal phases, demonstrating the self-organization and structure-property relationship in chiral LCs.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Jia-Yin Wang, Guigen Li, Wen-Juan Hao, Bo Jiang
Summary: A new asymmetric catalytic conjugate reduction method has been established for synthesizing enantioenriched cyclobuta[a]-naphthalen-4(2H)-ones using copper-bisphosphine complexes as catalysts, providing excellent regio- and enantioselectivities. This protocol is tolerant to a broad scope of substrates, exhibits high compatibility with various substituents, and offers excellent stereoselectivity.
Article
Chemistry, Multidisciplinary
Lu Qian, Xixia Tang, Yulei Wang, Guixia Liu, Zheng Huang
Summary: The use of a chiral (NCP)Ir complex as the precatalyst allows for the asymmetric transfer hydrogenation of diaryl ketones. This method is applicable to various ortho-substituted diaryl ketones and can be conducted in gram scale under mild reaction conditions.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Multidisciplinary Sciences
Congcong Yin, Ya-Fei Jiang, Fanping Huang, Cong-Qiao Xu, Yingmin Pan, Shuang Gao, Gen-Qiang Chen, Xiaobing Ding, Shao-Tao Bai, Qiwei Lang, Jun Li, Xumu Zhang
Summary: In this paper, an efficient anionic Ir catalyst for asymmetric hydrogenation of ketones is reported, which exhibits biocatalysis-like efficacy with high enantiomeric excess and turnover number. In industrial applications, this catalyst plays a significant role in a highly selective process route.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Tiao-Zhen Zhu, Pan-Lin Shao, Xumu Zhang
Summary: A highly efficient method for the synthesis of chiral secondary 2,2,2-trifluoroethanols has been developed, providing high yields and excellent enantioselectivities. The practicality of this method was demonstrated through the facile preparation of key intermediates of Odanacatib and LX-1301.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Juana M. Perez, Roxana Postolache, Marta Castineira Reis, Esther G. Sinnema, Denisa Vargova, Folkert de Vries, Edwin Otten, Luo Ge, Syuzanna R. Harutyunyan
Summary: Chiral Mn(I) complexes have been shown to activate H-P bonds, providing a general method for the hydrophosphination of internal and terminal alpha,beta-unsaturated nitriles. Metal-ligand cooperation, a previously unconsidered strategy for catalytic H-P bond activation, plays a key role in the mechanistic action of the Mn(I)-based catalyst. Computational studies support a stepwise mechanism for the hydrophosphination reaction and offer insights into the origin of enantioselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Tao Wang, Xiao-Yan Zhang, Yu-Cong Zheng, Yun-Peng Bai
Summary: A carbonyl reductase variant, SmCRM5, obtained from Serratia marcescens through structure-guided directed evolution, showed improved specific activity towards multiple substrates and high stereoselectivities in the asymmetric synthesis of gamma-/delta-lactones.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Victor Garcia-Vazquez, Pablo Martinez-Pardo, Alexandru Postole, A. Ken Inge, Belen Martin-Matute
Summary: This study developed a method for synthesizing chiral trifluoromethylated aliphatic amines, which involves organocatalytic isomerization and imine/enamine reduction to obtain compounds with two noncontiguous stereogenic centers in high yields and selectivities. The method is effective for primary amine substrates and provides a new pathway for synthesizing chiral trifluoromethylated scaffolds.
Article
Chemistry, Physical
Jitao Yang, Lijun Yao, Zheng Wang, Zheng Zuo, Siyuan Liu, Pengxiang Gao, Mingyang Han, Qingbin Liu, Gregory A. Solan, Wen-Hua Sun
Summary: A new chiral ligand, LPNN-1, was successfully used in Mn-catalyzed asymmetric transfer hydrogenation and asymmetric hydrogenation. The Mn-pincer complex Mn-1 showed better catalytic performance, leading to higher enantioselectivities. DFT calculations and experimental investigations proposed a possible mechanism for the Mn-catalyzed ATH.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Physical
Yunfan Yue, Tian Ma, Hexiang Qi, Yaqi Zhao, Xiaofan Shi, Yanhui Tang, Min Pu, Ming Lei
Summary: In this study, a series of bowl-shaped quadridentate ligands and their manganese catalysts were designed for the hydrogenation of unsaturated bonds using density functional theory. The calculated results suggest that the bowl-shaped structure of the ligands and their connection to the Si-N-Si-C-Si-C six-membered ring core significantly affect the catalytic activity and selectivity. This work provides theoretical insights for designing new transition metal catalysts.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Organic
Akram Hussain, Swamy Peraka, Dhevalapally B. Ramachary
Summary: We developed a sustainable three-component reductive amination protocol for the chemoselective coupling of optically active functionally rich donor-acceptor carbonyl-cyclopropanes with various amines. This catalytic selective reductive C-N coupling has wide advantages and generates chiral cyclopropane-containing amines with many applications in medicinal chemistry.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Organic
Chuanle Zhu, Yingying Cai, Huanfeng Jiang
Summary: Chiral sulfones, especially those compounds with sulfone groups directly connected to the chiral centers, are privileged building blocks in natural products and bioactive compounds. Various strategies have been developed for their asymmetric synthesis, including nucleophilic substitution, hydrosulfonation, cross-coupling reactions, and others, which are important for the synthesis of bioactive compounds.
ORGANIC CHEMISTRY FRONTIERS
(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.
Article
Chemistry, Physical
Shizuka Ito, Xianwei Wang, Ammara Waheed, Gao Li, Nobutaka Maeda, Daniel M. Meier, Shuichi Naito, Alfons Baiker
Summary: In the oxidation of benzyl alcohol to benzaldehyde on Ir-based catalysts, the influence of support materials Al2O3, CeO2, and TiO2 was studied. Among them, TiO2 exhibited high catalytic performance, while CeO2 showed poor performance. The formation of a titania overlayer after hydrogen pretreatment significantly affected the catalytic activity.
JOURNAL OF CATALYSIS
(2021)
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.
Review
Chemistry, Physical
Matthias S. Frei, Florentine L. P. Veenstra, David Capeder, Joseph A. Stewart, Daniel Curulla-Ferre, Antonio J. Martin, Cecilia Mondelli, Javier Perez-Ramirez
Summary: The paper introduces an integrated strategy to accelerate the design of multicomponent heterogeneous catalysts by studying the interface contributions of catalysts. Linear correlations between the methanol formation rate and the interface between the metal and the oxide are revealed through studying the high-pressure continuous-flow hydrogenation of CO and CO2 over Cu-ZnO catalysts. The current challenge lies in the preparation of model catalysts, which can be addressed through further development of nanotechnological tools.
Article
Chemistry, Physical
Thaylan P. Araujo, Arjun Shah, Cecilia Mondelli, Joseph A. Stewart, Daniel Curulla Ferre, Javier Perez-Ramirez
Summary: This study evaluated the sensitivity of In2O3 catalysts to CO, finding a decrease in methanol productivity for most catalysts except one. Controlled formation of oxygen vacancies and resistance to sintering were identified as key factors for activation, while a combination of CO/H2O-induced sintering and CO inhibition caused performance loss. Assessment with mixed CO2-CO feeds is crucial for designing industrially viable catalysts for sustainable methanol production.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2021)
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)