Article
Chemistry, Multidisciplinary
Brendan L. Hall, Connor J. Taylor, Ricardo Labes, Alexander F. Massey, Robert Menzel, Richard A. Bourne, Thomas W. Chamberlain
Summary: An automated continuous flow reactor system with inline analysis was developed for self-optimization of a nanoparticle-catalyzed reaction, achieving maximum conversion in under 2.5 hours. Data from this optimization was used to generate a kinetic model for predicting reaction outcomes under different conditions, potentially accelerating the development timeline for emerging catalysts.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Applied
Moreshwar B. B. Chaudhari, Prachi Gupta, Patricia Llanes, Miquel A. A. Pericas
Summary: The enantioselective Pictet-Spenlger reaction of tryptamines and diketo compounds catalyzed by a polymer-supported phosphoric acid (TRIP) has been achieved for the first time in continuous flow. A diverse library of quaternary tryptolines has been synthesized in 36-95% yield with 39-99% enantiomeric excess using this approach. The scalability of the reaction has been demonstrated in continuous flow, with a residence time of only 24 minutes. The robust immobilized catalyst has been recycled and reused multiple times in both batch and flow reactions. Synthesis of chiral precursors of Tadalafil, Iboga-type alkaloid (+)-Tabertinggine, and antimalarial spiroindolinones has been successfully achieved in both batch and continuous-flow reactions.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Nan Sun, Kai Zheng, Mingqiang Zhang, Guowen Zheng, Liqun Jin, Baoxiang Hu, Zhenlu Shen, Xinquan Hu
Summary: A mild Cu-catalysed Chan-Lam protocol has been developed for the synthesis of unsymmetrical aryl chalcogenides, including selenides and sulfides, in an aqueous micellar medium. The catalytic system consists of a CuBr catalyst, a water-soluble ligand, a surfactant, and air as the terminal oxidant. A diverse variety of diorganyl diselenides/disulfides could be coupled with various aryl, heteroaryl, and styryl boronic acids in water at ambient temperature to afford the corresponding aryl chalcogenide products in good to excellent yields. The aqueous phase can be recycled at least seven times by adding an additional half catalytic amount of CuBr during each subsequent cycle. UV-VIS spectral studies revealed the solubility of both hydrophobic diorganyl diselenides/disulfides and hydrophilic arylboronic acids in water with the help of the surfactant. Transmission electron microscopy studies showed the formation of nanomicelles under the reaction conditions.
Article
Multidisciplinary Sciences
Ji-Jun Chen, Jia-Heng Fang, Xuan-Yi Du, Jia-Yong Zhang, Jun-Qian Bian, Fu-Li Wang, Cheng Luan, Wei-Long Liu, Ji-Ren Liu, Xiao-Yang Dong, Zhong-Liang Li, Qiang-Shuai Gu, Zhe Dong, Xin-Yuan Liu
Summary: Unnatural chiral amines are in high demand in the pharmaceutical and agrochemical industries. This study presents a copper-catalysed method using chiral tridentate anionic ligands for highly selective N-alkylation of aliphatic amines. The method allows for the direct conversion of feedstock chemicals into unnatural chiral α-amino amides under mild conditions, demonstrating excellent enantioselectivity and functional group tolerance. The use of multidentate anionic ligands overcomes the issue of transition metal catalyst poisoning.
Article
Chemistry, Applied
Shuhao Zhou, Yunting Xin, Jiasheng Wang, Chengjun Wu, Tiemin Sun
Summary: A combination of continuous flow and batch experiments has been developed for the synthesis of tazobactam, improving procedure safety and efficiency. Under optimized conditions, the total yield of the target product reached 37.09%, higher than the 30.93% in batch experiments.Continuous flow method greatly reduces reaction time, improves safety, and increases yield.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2021)
Article
Chemistry, Multidisciplinary
Cloudius R. Sagandira, Agnes Z. Khasipo, Paul Watts
Summary: This study presents an isocyanate-free synthetic method for preparing the widely prescribed antidiabetic sulfonylurea drugs glipizide and glibenclamide at a multigram scale using continuous flow technology. Safety concerns regarding isocyanates in existing synthetic routes were addressed by utilizing N-carbamates synthesized in situ as safer alternatives. An overall yield of 80-85% was achieved for the semi-telescoped steps within a total residence time of less than 10 minutes.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Christian Heider, Alina Winter, Viktoria Voss, Dieter Vogt, Thomas Seidensticker
Summary: Combining a tubular flow reactor with a robust homogeneous catalyst enabled running the alcohol amination at unique conditions, i.e., very high temperatures at low residence times. Catalytic activities were thus increased to unprecedented values of >900 h(-1) in the synthesis of tertiary dimethylalkylamines directly from alcohols with excellent selectivities exceeding 99%. Furthermore, several alcohols could be converted to the desired tertiary amines.
Review
Chemistry, Multidisciplinary
Christopher P. Breen, Anirudh M. K. Nambiar, Timothy F. Jamison, Klavs F. Jensen
Summary: Synthetic chemistry has opened up new possibilities for innovation in key industries such as medicine, energy, and agriculture. Automation is challenging the traditional process of chemical synthesis, while continuous flow chemistry presents a flexible platform for automation. The merger of synthesis and automation is expected to democratize access to custom complex small molecules and accelerate the development of new synthetic protocols.
TRENDS IN CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yuki Saito, Ken Nishizawa, Benjamin Laroche, Haruro Ishitani, Shu Kobayashi
Summary: This study demonstrates the continuous-flow synthesis of (R)-tamsulosin without the need for the isolation or purification of any intermediates or byproducts. The synthesis was achieved through four catalytic transformations in a flow stream, resulting in a high yield and enantiomeric excess.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Thermodynamics
K. Sreelakshmi, G. Sandhya, G. Sarojamma, K. Vajravelu, Aj Chamkha
Summary: In this research, the assessment of entropy in the MHD flow of a hybrid nanofluid and a mono-nanofluid was explored. The effects of various physical parameters on the flow features were analyzed, and a comparison was made between the two types of nanofluids. The results validated the accuracy of the numerical method used and showed that the hybrid nanofluid had higher temperature and thermal diffusion rate compared to the mono-nanofluid.
JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY
(2022)
Article
Chemistry, Physical
Andrea Merenda, Samantha A. Orr, Yang Liu, Blanca Hernandez Garcia, Amin Osatiashtiani, Gabriel Morales, Marta Paniagua, Juan A. Melero, Adam F. Lee, Karen Wilson
Summary: In this study, a dual-catalyst bed configuration was developed to achieve efficient conversion of levulinic acid into gamma-Valerolactone (GVL). By utilizing sulfated zirconia (SZ) and ZrO2/SBA-15 as the Bronsted and Lewis acid catalysts, respectively, high conversion and selectivity were achieved in the esterification and hydrogenation reactions. The dual-bed system showed significantly higher productivity compared to the individual catalysts or their physical mixture.
Article
Chemistry, Multidisciplinary
Yong-Feng Cheng, Zhang-Long Yu, Yu Tian, Ji-Ren Liu, Han-Tao Wen, Na-Chuan Jiang, Jun-Qian Bian, Guo-Xiong Xu, Dan-Tong Xu, Zhong-Liang Li, Qiang-Shuai Gu, Xin Hong, Xin-Yuan Liu
Summary: The transition-metal-catalysed cross-coupling reaction has been widely used to construct carbon-carbon/heteroatom bonds. However, the development of heteroatom-heteroatom cross-couplings has been challenging. In this study, a new strategy using single-electron reductive elimination under Cu catalysis was demonstrated for enantioselective S-O coupling. This reaction showed its synthetic potential in preparing chiral alcohols, utilizing biomass-derived feedstock glycerol, and catalytic 4,6-desymmetrization of inositol. These results highlight the potential of enantioselective radical heteroatomic cross-coupling as a general chiral heteroatom-heteroatom bond formation strategy.
Article
Chemistry, Multidisciplinary
Qandeel Saleem, Milad Torabfam, Tuce Fidan, Hasan Kurt, Meral Yuce, Nigel Clarke, Mustafa Kemal Bayazit
Summary: This article presents the use of microwave-promoted continuous flow systems in nanoparticle synthesis, discussing the impact of various parameters on nanoparticle properties and the advantages over batch processing. It also analyzes different microwave continuous flow reactors and nanosynthesis routes, emphasizes the importance of numerical modeling, and looks ahead to future prospects of this technology.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2021)
Article
Chemistry, Multidisciplinary
Shang-Hai Yu, Tian-Jun Gong, Yao Fu
Summary: A cooperative Cu/Pd-catalysed borylallenylation of 2-trifluoromethyl-1,3-enynes with propargylic carbonates under mild reaction conditions was developed, providing facile and efficient access to conjugated bisallenes with a broad range of functional groups.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Pavol Lopatka, Michal Gavenda, Martin Markovic, Peter Koos, Tibor Gracza
Summary: This work describes the total synthesis of jaspine B using highly diastereoselective Pd(II)-catalysed carbonylative cyclisation for the preparation of crucial intermediates. New conditions involving the use of pBQ/LiCl and Fe(CO)(5) were developed, and the application of a flow reactor in large-scale preparation of key lactones was demonstrated.
Article
Chemistry, Multidisciplinary
Jona Merx, Kas J. Houthuijs, Hidde Elferink, Eva Witlox, Jasmin Mecinovic, Jos Oomens, Jonathan Martens, Thomas J. Boltje, Floris P. J. T. Rutjes
Summary: This study characterized cyclic N-acyliminium ions in the gas phase through collision induced dissociation tandem mass spectrometry and infrared ion spectroscopy, providing valuable insights into their conformations through comparison of DFT calculated spectra with experimentally observed IR spectra.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Review
Chemistry, Medicinal
Marnix R. van der Kolk, Mathilde A. C. H. Janssen, Floris P. J. T. Rutjes, Daniel Blanco-Ania
Summary: Cyclobutanes, with their unique structure, offer various benefits in medicinal chemistry, such as improving drug candidate properties through replacement of alkenes and larger cyclic systems.
Article
Chemistry, Organic
Wouter A. Remmerswaal, Kas J. Houthuijs, Roel van de Ven, Hidde Elferink, Thomas Hansen, Giel Berden, Herman S. Overkleeft, Gijsbert A. van der Marel, Floris P. J. T. Rutjes, Dmitri Filippov, Thomas J. Boltje, Jonathan Martens, Jos Oomens, Jeroen D. C. Codee
Summary: The stereoselective introduction of glycosidic bonds is crucial for oligosaccharide synthesis. Among various strategies, the participation of neighboring or distal acyl groups is commonly used to achieve stereoselectivity. In this study, the use of DMNPA protection group is shown to enhance stereoselectivity compared to other acyl groups. Through glycosylation reactions and infrared ion spectroscopy, it is revealed that the stereoselectivity induced by DMNPA group is attributed to the formation of a stable dioxolenium ion.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biotechnology & Applied Microbiology
Magda A. Rogowska-van der Molen, Dmitrii Nagornii, Silvia Coolen, Rob M. de Graaf, Tom Berben, Theo van Alen, Mathilde A. C. H. Janssen, Floris P. J. T. Rutjes, Robert S. Jansen, Cornelia U. Welte
Summary: Plants have evolved chemical defense mechanisms to deter herbivores, including the production of plant toxins like nitropropionic acid (NPA). In this study, a bacterium isolated from the gut of the Southern green shield bug was found to degrade NPA and its metabolic pathway was identified. The discovery of NPA degradation pathways by environmental bacteria opens up new possibilities for pretreating contaminated food sources and utilizing understudied enzymes in biotechnology.
APPLIED AND ENVIRONMENTAL MICROBIOLOGY
(2022)
Article
Biology
Jona Merx, Rianne E. van Outersterp, Udo F. H. Engelke, Veronique Hendriks, Ron A. Wevers, Marleen C. D. G. Huigen, Huub W. A. H. Waterval, Irene M. L. W. Korver-Keularts, Jasmin Mecinovie, Floris P. J. T. Rutjes, Jos Oomens, Karlien L. M. Coene, Jonathan Martens, Thomas J. Boltje
Summary: Biomarkers of hyperprolinemia type II (HPII) were identified and characterized using metabolomics and spectroscopy methods. These biomarkers showed similar metabolic signatures as in patients with hyperprolinemia type I (HPI) and pyridoxine-dependent epilepsy, and could differentiate HPII from HPI.
COMMUNICATIONS BIOLOGY
(2022)
Article
Chemistry, Multidisciplinary
Daan Sondag, Luuk Maartense, Heleen de Jong, Frank F. J. de Kleijne, Kimberly M. Bonger, Dennis W. P. M. Lowik, Thomas J. Boltje, Jan Dommerholt, Paul B. White, Daniel Blanco-Ania, Floris P. J. T. Rutjes
Summary: This study reports a scalable and accessible synthesis method for a new bioorthogonal difunctionalized TCO, demonstrating its potential applications in efficient payload release and cellular toxicity.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Daan Sondag, Stijn Verhoeven, Dennis W. P. M. Lowik, Mark van Geffen, Cornelis van't Veer, Waander L. van Heerde, Thomas J. Boltje, Floris P. J. T. Rutjes
Summary: The blood coagulation cascade is a complex process involving multiple enzymes, cofactors, and substrates, and its dysregulation can lead to bleeding disorders and thrombosis. This review summarizes the key proteases involved in blood clot formation and fibrinolysis, their recognition and hydrolysis of endogenous peptide sequences, and the use of synthetic peptide probes for measuring their activity. The information provided in this review can contribute to the development of novel anticoagulant therapies and specific substrates for point-of-care diagnosis of coagulation pathologies.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Lennart Dreisewerd, Ruud L. E. G. Aspers, Martin C. Feiters, Floris P. J. T. Rutjes, Marco Tessari
Summary: Differentiating and quantifying enantiomers is crucial in pharmaceutical, chemical, and food industries. However, traditional methods are time-consuming and require complex techniques and expertise. We propose a new approach using non-hydrogenative parahydrogen-induced hyperpolarization and nuclear magnetic resonance, which allows for direct detection, discrimination, and quantification of enantiomers in complex mixtures like biofluids and food extracts, without the need for prior isolation or functionalization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Multidisciplinary
Daan Sondag, Stijn Verhoeven, Dennis W. P. M. Lowik, Mark van Geffen, Cornelis van't Veer, Waander L. van Heerde, Thomas J. Boltje, Floris P. J. T. Rutjes
Summary: The blood coagulation cascade is a complex physiological process that involves multiple enzymes, cofactors, and substrates, leading to clot formation. Serine proteases play a crucial role, and abnormalities in their activity can result in life-threatening bleeding disorders and thrombosis. This review summarizes the important proteases involved in blood coagulation and fibrinolysis, their recognition and hydrolysis of endogenous peptide sequences, and synthetic peptide probes for measuring their activity. The information in this review can contribute to the development of novel anticoagulant therapies and specific substrates for point-of-care diagnosis of coagulation pathologies.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Organic
Stefan van Rootselaar, Evert Peterse, Daniel Blanco-Ania, Floris P. J. T. Rutjes
Summary: Piperidine alkaloids are a type of alkaloid characterized by a six-membered nitrogen-containing heterocycle. They are mainly found in plants and have interesting biological and pharmacological activities. The synthesis of piperidine alkaloids and their derivatives is important for drug discovery due to their low natural abundance.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Medicinal
Tom Dekker, Mathilde A. C. H. Janssen, Christina Sutherland, Rene W. M. Aben, Hans W. Scheeren, Daniel Blanco-Ania, Floris P. J. T. Rutjes, Maikel Wijtmans, Iwan J. P. de Esch
Summary: The success of fragment-based drug discovery (FBDD) is closely related to library design. A workflow in KNIME software has been created to guide the design of fragment libraries, considering chemical diversity and novelty of the fragments, as well as their three-dimensional (3D) character. This design tool can create large and diverse libraries or select representative compounds to enrich existing libraries.
ACS MEDICINAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Mathijs J. Bouma, Ruud L. E. G. Aspers, Marco Tessari, Floris P. J. T. Rutjes, Roan Fraser, Martin C. Feiters
Summary: Non-hydrogenative Para-Hydrogen Induced Hyperpolarization (nhPHIP) is a Nuclear Magnetic Resonance (NMR) hyperpolarization technique that has been used to analyze complex biological samples containing amino acids. A computational study based on Density Function Theory (DFT) was performed to analyze the structures and properties of the relevant catalysts and amino acids. The results provided detailed explanations for the observed trends in thermal NMR experiments.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Wouter A. Remmerswaal, Kas J. Houthuijs, Roel van de Ven, Hidde Elferink, Thomas Hansen, Giel Berden, Herman S. Overkleeft, Gijsbert A. van der Marel, Floris P. J. T. Rutjes, Dmitri V. Filippov, Thomas J. Boltje, Jonathan Martens, Jos Oomens, Jeroen D. C. Codee
Summary: The stereoselective introduction of glycosidic bonds is crucial for oligosaccharide synthesis, and the participation of neighboring or distal acyl groups is commonly used for stereoselectivity control. A recent study found that the 2,2-dimethyl-2-(ortho-nitrophenyl)acetyl (DMNPA) protection group exhibited enhanced stereoselective steering compared to other acyl groups. Through glycosylation reactions and infrared ion spectroscopy (IRIS) combined with isotopic labeling and population analysis, it was determined that the enhanced stereoselectivity of the DMNPA group is not a result of the direct participation of the nitro moiety, but rather due to the stabilization of a dioxolenium ion formed by the nitro group.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Zi-Ye Liu, Qian-Yu Wang, Ji-Ming Hu
Summary: In this study, a layered carbon dot composite catalyst (NiFe LDH@CDs) was prepared using a one-step coprecipitation method, without the need for heating or hydrothermal treatment. The CD-functionalized catalyst facilitated rapid charge transfer and accelerated the oxygen evolution reaction. Additionally, the heterojunction structure formed between NiFe LDH and CDs efficiently suppressed photoelectron-hole recombination.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Rohit Kumar, Ankit Kumar Srivastava, Palaniyappan Nagarasu, Vedichi Madhu, Ekambaram Balaraman
Summary: We designed and synthesized a NN-CoII bidentate complex and used it for the amination of alcohols under mild and solventless conditions. The complex exhibited good reactivity towards both primary and sterically hindered secondary alcohols, providing high yields of amines. The pyrazole moiety in the ligand played a crucial role in the reaction. Furthermore, we demonstrated the reusability of the complex as a homogeneous cobalt catalyst.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Shivanand Chettri, Liang-Ting Wu, Sagarmani Rasaily, Debesh Sharma, Bikram Gurung, Rajani Dewan, Sudarsan Tamang, Jyh-Chiang Jiang, Anand Pariyar
Summary: Replicating the enzymatic surface microenvironment in vitro is challenging, but constructing an analogous model could facilitate our understanding of surface effects and aid in developing an efficient bioinspired catalytic system. In this study, five unique Cu2O morphologies were generated, and the surface morphology variations were found to be a consequence of differences in the exposure of low-index facets. The reactivity of Cu2O was found to be influenced by the proportion of {110} planes, with r-Cu2O exhibiting the highest reactivity.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Yong Tang, Jianhao Qiu, Dingliang Dai, Guanglu Xia, Lu Zhang, Jianfeng Yao
Summary: Defect engineering has been shown to improve the photocatalytic performance. This study investigated the use of defect-rich UiO-66-NH2 wrapped by ZnIn2S4 as a catalyst for photocatalytic H2O2 production. The defects in UiO-66-NH2 enhanced O-2 adsorption and charge separation, leading to higher H2O2 yield. The insights from this work can advance the research in defect engineering of MOFs and photocatalytic H2O2 synthesis.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Ruiyang Qu, Shuxin Mao, Jana Weiss, Vita A. Kondratenko, Evgenii V. Kondratenko, Stephan Bartling, Haifeng Qi, Annette-Enrica Surkus, Kathrin Junge, Matthias Beller
Summary: The hydrogenation of amides, a challenging reaction usually performed at high temperatures, has been achieved under milder conditions using a new Pt-MoOx/TiO2 catalyst. This catalyst system enables the selective hydrogenation of various amides and imides.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Xiaoran Niu, Ao Wang, Lei Tong, Lei Wang, Yuan Kong, Chenliang Su, Hai-Wei Liang
Summary: This study introduces a novel intermetallic PdCu3 catalyst supported on defective nanodiamond-graphene (ND@G), which exhibits high selectivity (95%) and remarkable activity (turnover frequency: 2940 h(-1)), six times higher than that of the commercial Lindlar catalyst.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Review
Chemistry, Physical
Zhiyuan Zheng, Yiming Yue, Hongying Zhuo, Qinggang Liu, Yanqiang Huang
Summary: This review presents the recent research advances on single-atom catalysis for deep reduction of CO2. Detailed introductions and summaries were classified into three categories based on proton-coupled multi-electron transfer approaches: strengthening metal-support interaction, rational design and regulation of coordination environment, and development of SACs with multi-atom active sites. The challenges and future research directions in the field of SACs for CO2 reduction are also proposed.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
Shiv Kumar, Paramita Datta, Anup Bhunia, Swadhin K. Mandal
Summary: This article reports a transition-metal-free process for in situ denitrogenation of tosylhydrazones, resulting in the production of various sulfones. The authors used a phenalenyl-based odd alternant hydrocarbon as a photoredox catalyst, which acted as a potent oxidant to facilitate the denitrogenation reaction. The method showed wide functional-group tolerance and high yields, making it suitable for late-stage modification of natural products.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
Article
Chemistry, Physical
L. A. Luque-Alvarez, J. Gonzalez-Arias, F. Romero-Sarria, T. R. Reina, L. F. Bobadilla, J. A. Odriozola
Summary: Currently, the production of acetic acid through the carbonylation reaction of methanol has limitations, leading to the exploration of alternative methods using heterogeneous catalysts. This study investigates the methanol carbonylation reaction over a Cu-H-MOR catalyst and proposes a reaction mechanism based on the catalytic behavior and performance of the catalyst. The results provide insights into the reaction mechanism and the involvement of acid and redox centers.
CATALYSIS SCIENCE & TECHNOLOGY
(2024)
