Review
Chemistry, Multidisciplinary
Purushothaman Rajeshwaran, Jonathan Trouve, Khalil Youssef, Rafael Gramage-Doria
Summary: The Wacker reaction is a significant industrial transformation that oxidizes olefins to ketones. However, it typically requires expensive palladium catalysts, which has led to the development of Wacker-type processes that avoid their use, allowing for more sustainable procedures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Ruyi Zhong, Puwei Wu, Qi Wang, Xiting Zhang, Lei Du, Yunhua Liu, Huakang Yang, Meng Gu, Z. Conrad Zhang, Limin Huang, Siyu Ye
Summary: Recently, defective cobalt oxide hydrate (CoOxHy) nanosheets with abundant oxygen vacancies and high porosity were synthesized through room-temperature reductive treatments. These nanosheets exhibited improved catalytic activity and selectivity for the electrocatalytic oxidation reaction of 5-hydroxymethylfurfural (HMFOR) for 2,5-furandicarboxylic acid (FDCA) production. The simultaneous regulation of oxygen vacancies and porosity of metal oxide/hydroxide catalysts by facile reductive treatments was highlighted as an efficient strategy for electrochemical biomass conversion.
Article
Chemistry, Multidisciplinary
Luis M. Aguirre Quintana, Yan Yang, Arun Ramanathan, Ningxin Jiang, John Bacsa, Laurent Maron, Henry S. La Pierre
Summary: The study investigates the reactivity of complexes with nitrous oxide, S-8, or Se-0, revealing different reactivity of Fe complexes and inertness of Co complexes.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Jiahui Ji, Qingyun Yan, Pengcheng Yin, Shinya Mine, Masaya Matsuoka, Mingyang Xing
Summary: A CoS2-x mixed with Fe2+ system was developed for the sustained release of singlet oxygen (O-1(2)) through ultrasonic treatment, effectively degrading various organic pollutants. This system can efficiently degrade organic pollutants for up to 30 days, surpassing the current CuPx system by a significant margin.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Ashley Love, Darren S. Lee, Gabriele Gennari, Richard Jefferson-Loveday, Stephen J. Pickering, Martyn Poliakoff, Michael George
Summary: This study reports the development of a small footprint continuous electrochemical Taylor vortex reactor capable of processing kilogram quantities of material per day. By controlling the size of the annular gap and the rotation speed of the electrode, optimization of substrate conversion and product selectivity can be achieved.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2021)
Article
Multidisciplinary Sciences
Tristan von Muenchow, Suman Dana, Yang Xu, Binbin Yuan, Lutz Ackermann
Summary: Enantioselective oxidation reactions typically rely on costly transition metals and stoichiometric amounts of chemical oxidants. This study demonstrates a sustainable alternative by using electrocatalysis, specifically the hydrogen evolution reaction (HER), in place of a chemical oxidant. The use of cobalt catalyst for asymmetric oxidation enables highly enantioselective aryl carbon-hydrogen bond (C-H) activation reactions, leading to the synthesis of chiral compounds. Additionally, cobalt-mediated electrocatalysis allows for selective desymmetrization through dehydrogenative C-H activation reactions, facilitating the preparation of sterically complex phosphorus (P)-stereogenic compounds.
Article
Polymer Science
Michael Zanon, Laura Montalvillo-Jimenez, Raquel Cue-Lopez, Enrique Martinez-Campos, Marco Sangermano, Annalisa Chiappone, Paula Bosch
Summary: The rise of 3D printing in the medical field has opened up new possibilities for creating artificial tissues/organs using a patient's own cells, potentially overcoming the lack of tissue donors and reducing the risk of tissue rejection. This study introduces a fully functionalized alginate ink for digital light processing (DLP) printers, offering a more biocompatible alternative to current 3D printing materials. The ink demonstrates good processability and geometry fidelity, making it suitable for tissue engineering applications.
Article
Chemistry, Multidisciplinary
Martin Linden, Silja Hofmann, Felix N. Weber, Robin M. Baer, Sherif J. Kaldas, Mark J. Ford, Siegfried R. Waldvogel
Summary: To demonstrate the technical application potential of electrochemical reactions, we developed a synthetic method to access the commercially available herbicide safener mefenpyr-diethyl. The target compound was synthesized via the (E)- or (Z)-hydrazone in a simple undivided electrolysis cell with non-hazardous aqueous sodium iodide as supporting electrolyte and mediator. Environmentally benign solvents or solvent-free conditions ensure a sustainable process and excellent recycling of the excess reagents. Finally, scale-up to the hectogram scale was performed with good to excellent yield.
Article
Chemistry, Applied
M. Angeles Stegmayer, Silvia Irusta, Eduardo E. Miro, Viviana G. Milt
Summary: Co, Ce and Co-Ce nanofibers were synthesized by electrospinning method and applied to gas-solid and solid-solid-gas reactions. Different activity trends were observed in CO oxidation and combustion of diesel soot, with Co-Ce nanofibers showing the highest activity for soot combustion and Co exhibiting the highest activity for CO oxidation. The temperature range for maximum combustion rate was narrow for soot combustion and wider for CO oxidation. The high activity for soot oxidation was attributed to multiple contact points between fibers and soot particles, while the trend observed for CO oxidation was related to the higher redox capacity of Co.
Article
Chemistry, Multidisciplinary
Ryan M. Kirk, Anthony F. Hill
Summary: This study reports the first examples of late transition metal eta(5)-arsolyls serving as ditopic donors to extraneous metal centres through both conventional and polar-covalent interactions.
Article
Chemistry, Organic
Chengcheng Yuan, Xiangxing Huang, Yaqi Qiao, Wenjing Guan, Chengkou Liu, Zheng Fang, Yuguang Li, Kai Guo
Summary: In this study, a catalyst- and oxidant-free direct switchable electrosynthesis of non-deaminated and deaminated furoquinones was developed and scaled up in both batch and continuous-flow modes. Despite a significant decrease in yield with only a two-fold increase in substrate amount in the batch mode, the continuous-flow reactor achieved good yields and steady production. Furthermore, continuous flow electrosynthesis showed higher production rates at higher currents with lesser electrolyte usage. Higher substrate concentrations were compatible, contributing to solvent economy. Therefore, the continuous-flow electrosynthesis reactor demonstrated promising scalability potential.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Biochemistry & Molecular Biology
Hana Nur Fitriana, Sangmin Lee, Hui Su Kim, Jiye Lee, Yurim Lee, Jin-Suk Lee, Hyojung Park, Chang Hyun Ko, Sung Yul Lim, Soo Youn Lee
Summary: CO2 can be converted into organic acids and carotenoids by photoautotrophic bacteria in the MES reactor. Introducing cobalt-phosphate-assisted water oxidation at the anode can improve the performance of MES.
BIOELECTROCHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Xiaoyang Fu, Chengzhang Wan, Yu Huang, Xiangfeng Duan
Summary: This minireview provides a brief introduction to the fundamental challenges associated with anode alcohol oxidation reaction (AOR) in alkaline direct alcohol fuel cells (ADAFCs), as well as the key performance metrics and evaluation protocols for benchmarking AOR electrocatalysts. Recent advances in noble-metal based AOR electrocatalysts, such as Pt, Pd, and Rh, are summarized with a focus on design criteria for improving specific activity and electrochemical surface area to achieve high mass activity and long term durability. Strategies to enhance Faradaic efficiency and reduce overpotential are also discussed. The article concludes with a brief perspective on future challenges and opportunities.
ADVANCED FUNCTIONAL MATERIALS
(2022)
Review
Chemistry, Multidisciplinary
Wangsheng Liu, Lin Hao, Junmin Zhang, Tingshun Zhu
Summary: Electrosynthesis has gained more attention recently for its potential in replacing chemical oxidants or reductants in molecule-electrode electron transfer. Sulfonyl compounds have been found as practical precursors of several radicals, and electrochemical redox reactions offer green and efficient pathways for activating these compounds.
Article
Chemistry, Physical
Ram Krishna Hona, Surendra B. Karki, Tengfei Cao, Rohan Mishra, George E. Sterbinsky, Farshid Ramezanipour
Summary: A water-splitting electrocatalyst based on earth-abundant metals, CaSrFe0.75Co0.75Mn0.5O6-delta (CSFCM), shows high activity, stability, and the ability to catalyze both oxygen and hydrogen evolution reactions effectively in various conditions. Its catalytic activity is intrinsic without the need for additional processing, making it a good benchmark compound for future studies of electrocatalytic parameters. Results suggest that systematic structural design and maximizing the number of free e(g) carriers are key factors in enhancing electrocatalytic activity.
Review
Chemistry, Multidisciplinary
Shuo-Qing Zhang, Li-Cheng Xu, Shu-Wen Li, Joao C. A. Oliveira, Xin Li, Lutz Ackermann, Xin Hong
Summary: In recent years, there has been a significant increase in the application of machine learning in the field of chemistry, showcasing the potential of data-driven prediction of synthesis performance. This minireview summarizes the latest techniques and designs in synthetic performance prediction, emphasizing the importance of incorporating chemical knowledge in machine learning. It hopes to inspire chemists to revisit the digitalization and computerization of organic chemistry principles.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Silvia Cattani, Andrea Secchi, Lutz Ackermann, Gianpiero Cera
Summary: Iron-catalysed C-H alkylations with alkenes on benzamides were achieved using N-triazole assistance. The regioselectivity can switch from linear to branched depending on the nature of the olefin. This approach allows for the synthesis of a variety of decorated benzamides with high levels of chemo-, regio-, and site-selectivity.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Yan Zhang, Zhenzhi Cai, Svenja Warratz, Chanchan Ma, Lutz Ackermann
Summary: In recent years, electrochemical oxidative reactions using radical intermediates have become an environmentally friendly and powerful method for the formation of C-E (E = C, N, S, Se, O and Hal) bonds through single-electron transfer processes at the electrodes. This minireview focuses on the recent advances in electrooxidation and radical reactions, particularly concerning radical additions onto alkynes, until June 2022.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Xinran Chen, Hasret Can Guelen, Jun Wu, Zi-Jing Zhang, Xin Hong, Lutz Ackermann
Summary: Ruthenium-catalyzed sigma-bond activation-assisted meta-C-H functionalization has gained significance in the formation of distal C-C bonds. However, the lack of mechanistic studies has hindered a complete understanding of the site-selectivity and reaction pattern. In this study, computational investigations were conducted on ruthenium-catalyzed C-H functionalization using alkyl bromides and aryl bromides. Monocyclometalated ruthenium(II) complexes were identified as the active species, with inner-sphere single electron transfer (ISET) facilitating the activation of organic bromides. The competition between reductive elimination and radical coupling determines the site-selectivity, which was further predicted using a multilinear regression model validated by experiments.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yan Zhang, Chunhang Zhao, Chanchan Ma, Zhenzhi Cai, Lutz Ackermann, Sven Trienes
Summary: We describe a mechanistically distinct approach using photoinduced carbon-carbon (C-C) activation/ring-opening to access gamma,delta-unsaturated aldehydes from methylenecyclobutanols and sulfonyl chlorides by strain release. The sulfonyl motif on the products was easily removed by another photocatalytic process, enabling the concise assembly of the natural product alatanone A. Our approach demonstrates versatile functional group tolerance, ample substrate scope, and scalability, and represents a conceptually distinct alternative to existing approaches for remote 1,4-diversifications, with a double bond remaining in the obtained products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Shan Chen, Binbin Yuan, Yulei Wang, Lutz Ackermann
Summary: By difunctionalization of nonactivated alkenes, twofold distal C-H functionalization was achieved, allowing rapid access to multifunctionalized molecules. The multicomponent ruthenium-catalyzed remote 1,n-difunctionalization (n=6,7) of nonactivated alkenes with fluoroalkyl halides and heteroarenes in a modular manner was reported. This method provided mild conditions, unique selectivity, and broad substrate scope, and featured a domino process for twofold remote C(sp(2))-H/C(sp(3))-H activation with the sequential formation of three different carbon-centered radicals. A plausible mechanism was proposed based on detailed experimental and computational studies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jun Wu, Wen Wei, Julia Poehlmann, Rajeshwaran Purushothaman, Lutz Ackermann
Summary: In this study, a ruthenium(II)-catalyzed multicomponent Domino reaction was reported, which enables the efficient synthesis of structurally diversified C-alkyl glycosides in a single step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Dingyi Wang, Binbin Yuan, Jiawei Xu, Lutz Ackermann
Summary: In this study, an electrochemical strategy was used to achieve the dual functionalization of unactivated alkenes through an intramolecular migration process. This strategy eliminated the need for sacrificial chemical oxidants and noble-metal catalysts, and the reactions were carried out under mild conditions. The electrochemistry enabled the migration of (hetero)aryl groups, leading to the formation of alkenyl/alkynyl-migration products. The reaction mechanism was established through experiments and computations.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Editorial Material
Chemistry, Organic
Lutz Ackermann, Song Lin
Summary: The field of organic electrosynthesis and electrocatalysis has experienced a remarkable revival in recent years. Electrochemistry, as an unconventional reaction tool, has allowed synthetic chemists to innovate novel transformations, advance new synthetic strategies, and enhance the sustainability of organic synthesis.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Kui Zeng, Ruhuai Mei, Sebastian Dechert, Lutz Ackermann, Kai Zhang
Summary: This study reports a recyclable stereoauxiliary aminocatalytic approach for the efficient one-pot synthesis of desired trisubstituted indolizine-2-carbaldehydes via [3+2] annulations of acyl pyridines and alpha,beta-unsaturated aldehydes, using aminosugars derived from biomass. Control experiments confirm the stereoauxiliary effect favored by the beta-anomer of D-glucosamine. Moreover, polymeric chitosan containing predominantly beta-D-anhydroglucosamine units shows excellent catalytic performance and can be used for large-scale synthesis and catalytic cycling experiments. Thus, this approach advances the existing methodologies and provides a rich library of indolizine-2-aldehydes, which can be used for late-stage diversification and targeted modifications of bioactive molecules or drugs.
COMMUNICATIONS CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Yulei Wang, Suman Dana, Hao Long, Yang Xu, Yanjun Li, Nikolaos Kaplaneris, Lutz Ackermann
Summary: Late-stage functionalization (LSF) is a powerful strategy to accelerate the development of medicinally relevant compounds, crop protecting agents, and functional materials. Electrochemical late-stage functionalization (eLSF) has emerged as an environmentally friendly platform and has gained significant momentum in the past decade.
Article
Chemistry, Multidisciplinary
Elisa Y. Lai, Binbin Yuan, Lutz Ackermann, Magnus J. Johansson
Summary: In this study, a new method for directed ruthenium-catalyzed C-H aminocarbonylation has been developed under mild conditions through high-throughput experimentation. This method allows the introduction of special amide functional groups and is applicable to various substitution patterns and different weakly Lewis basic directing groups in anilides.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Meteorology & Atmospheric Sciences
S. P. Alexander, A. Protat, A. Berne, L. Ackermann
Summary: Antarctic precipitation, especially within the boundary layer, is poorly characterized and understood due to limited surface-based remote sensing observations. This study used cloud and precipitation remote-sensing instruments to characterize snowfall over Davis. The results reveal the relationship between virga and wind conditions, particle aggregation at certain temperatures, and the sublimation of snowfall mass at different altitudes. These findings contribute to a better understanding of snowfall in the Antarctic region.
JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES
(2023)
Article
Chemistry, Physical
Julia Struwe, Lutz Ackermann
Summary: In recent years, photoelectrocatalysis has become more and more viable for molecular synthesis. However, there is still a lack of detailed comparison among different catalysts for the undirected C-H functionalization of arenes. To address this, more than a dozen different mediators were utilized to compare their efficacies in the trifluoromethylation of (hetero-)arenes.
FARADAY DISCUSSIONS
(2023)
Article
Chemistry, Multidisciplinary
Isaac Maksso, Ramesh C. Samanta, Yifei Zhan, Kai Zhang, Svenja Warratz, Lutz Ackermann
Summary: The chemical up-cycling of polymers into value-added materials provides an opportunity for a circular economy. This study demonstrates the selective up-cycling of polystyrenes and polyolefins to C(sp(3))-H azidated materials through chemo-selective mangana-electrocatalysis. The functionalized polymers obtained showed high mass retention and functionalization. The electrocatalysis approach proved to be scalable and has implications for a green hydrogen economy.