Article
Chemistry, Multidisciplinary
Raphael Robidas, Claude Y. Legault
Summary: A mechanism is proposed to explain the formation of benzobicyclo[3.2.0]heptane derivatives from 1,7-enyne derivatives bearing a terminal cyclopropane, which has been previously reported.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Froze Jameel, Matthias Stein
Summary: In the global effort to combat climate change, the design and development of new procedures for complex chemical multi-step reactions play a crucial role in the transformation of the chemical industry. Solvent effects on thermodynamics and kinetics are important considerations, with various roles including promoting intermediate formation but also compromising overall pathways. Solvent coordination is critical for the activity of reducing catalysts, impacting regioselectivity and reaction rates in complex multi-step reactions.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Xiong Xiao, Zhi-Xiang Yu
Summary: The research presents a highly enantioselective intramolecular [3+2] cycloaddition of yne-alkylidenecyclopropanes using a cheap Co catalyst and commercially available chiral ligand, achieving up to 92% enantiomeric excess. Experimental evidence suggests cationic cobalt(I) species as the catalytic species, with a mechanism differing from previous [3+2] reactions of ACPs.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Chuncheng Lin, Weihao Wan, Xueting Wei, Jinzhu Chen
Summary: Co nanoparticles encapsulated in N-doped carbon nanotubes (Co@NC900) have been investigated as a potential substitute for precious Pt-group catalysts in hydrogenative heterocyclization reactions. Co@NC900 demonstrates efficient catalytic activity for the hydrogenative coupling of 2-nitroaniline to benzaldehyde, with >99% yield at ambient temperature in a single step. The catalyst is easily recoverable and recyclable, with kinetic experiments suggesting that hydrogenation is the rate-determining step, with an apparent activation energy of 41 +/- 1 kJ mol(-1). Theoretical investigations reveal the mechanism by which Co@NC900 activates both H-2 and the nitro group of 2-nitroaniline, providing insights for the green and efficient synthesis of heterocyclic compounds.
Article
Chemistry, Multidisciplinary
Philip Andreetta, Robert T. Martin, Charafa Souilah, Angel Renteria-Gomez, Zhihui Song, Yas Khorramshahi Bayat, Sergei Ivlev, Osvaldo Gutierrez, Alicia Casitas
Summary: In this study, a cobalt(I)-catalyzed regioselective allylic alkylation reaction of tertiary allyl carbonates with 1,3-dicarbonyl compounds was developed. A series of tetrahedral cobalt(I) complexes with commercially available bidentate bis(phosphine) ligands were synthesized and investigated as catalysts. The results showed that one specific catalyst exhibited high yields and excellent regioselectivity for the branched product in the alkylation of various tertiary allyl carbonates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Sara Lopez-Resano, Sara Martinez de Salinas, Felipe A. Garces-Pineda, Andrea Moneo-Corcuera, Jose Ramon Galan-Mascaros, Feliu Maseras, Monica H. Perez-Temprano
Summary: The potential access to Co-IV species to promote transformations challenging at Co-III in Cp*Co-catalyzed C-H functionalization reactions remains underexploited. We reveal the participation of Cp*Co-IV species in a Cp*Co-mediated C-S bond-reductive elimination through a combined experimental and computational strategy. These studies support the intermediacy of high-valent Cp*Co species in C-H functionalization reactions, particularly when involving nucleophilic coupling partners under oxidative conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Xiangyu Meng, Rui Li, Junyi Yang, Shiming Xu, Chenchen Zhang, Kejia You, Baochun Ma, Hongxia Guan, Yong Ding
Summary: Photosynthesis is considered the most crucial biochemical reaction in nature, as it regulates the stable levels of O-2 and CO2 in the atmosphere. Researchers have developed an artificial photosynthesis model reaction that converts CO2 to CO using photochemical methods. The study demonstrates that efficient electron transfer plays a significant role in achieving excellent photocatalytic CO2 reduction performance. Furthermore, the researchers explored the catalytic mechanism of the CO2 reduction reaction.
CHINESE JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Inorganic & Nuclear
Feda'a M. Al-Qaisi, Abdussalam K. Qaroush, Ibrahim K. Okashah, Ala'a F. Eftaiha, Petra Vasko, Fatima Alsoubani, Timo Repo
Summary: By following green chemistry principles, a zinc curcumin complex was synthesized and used as a sustainable catalyst for the synthesis of cyclic carbonate from CO2 and epoxides. The complex exhibited outstanding catalytic activity and showed potential for the synthesis of renewable carbonates.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Jesus A. Avendano-Villarreal, Fabio G. Delolo, Artur V. Granato, Elena V. Gusevskaya, Eduardo N. dos Santos
Summary: A new and efficient method was developed to transform naturally occurring 1-propenylbenzenes into 2-arylpropylamines. This method involved a one-pot ethenolysis/hydroaminomethylation reaction and required careful selection of reaction conditions to achieve high yields. By adjusting the molar ratio of the catalysts, the interference between ethenolysis and hydroaminomethylation catalysts was avoided, resulting in the synthesis of nine 2-arylpropylamines with yields ranging from 75-93%.
Article
Chemistry, Multidisciplinary
Tanuja Tewari, Rohit Kumar, Amol C. Chandanshive, Samir H. Chikkali
Summary: Metal-catalyzed hydroformylation and hydrogenation heavily rely on ligands, with phosphorus ligands playing a pivotal role. This account presents three distinct classes of phosphorus ligands, their synthesis, performance in reactions, and the latest developments in iron-catalyzed hydroformylation of alkenes. The use of phosphines enabled iron-catalyzed hydroformylation under mild conditions, demonstrating the central role of phosphorus ligands in industrially relevant transformations.
Article
Chemistry, Multidisciplinary
Alexander G. Sturm, Uhut S. Karaca, Myron Heinz, Thorsten Felder, Kenrick M. Lewis, Norbert Auner, Max C. Holthausen
Summary: In this study, an energetically and environmentally benign synthetic protocol for the highly selective conversion of SiCl4 to HSiCl3 was reported. The protocol utilized organohydridosilanes as recyclable hydrogen transfer reagents and onium chlorides as efficient catalysts. This same protocol was also used for the quantitative conversion of higher oligosilane residues generated from Siemens processes.
Review
Chemistry, Multidisciplinary
Peng Wang, Huan Liu, Da Yang
Summary: This article introduces the principle and application of tandem hydroformylation reaction, and presents several common catalyst systems and efficient synthesis methods. The future prospects of this reaction are also discussed.
PROGRESS IN CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Tasneem Elkoush, Natasha D. Reich, Michael G. Campbell
Summary: In the past two decades, there has been a significant increase in the number of synthetically useful transformations catalyzed by silver, with dinuclear silver species commonly emerging as a key feature in these reactions. Understanding the role of dinuclear silver complexes in homogeneous catalysis can aid in the development of improved design principles for silver catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Shiqiang Huang, Hang Zhang, Jiahao Zhuang, Mingyue Zhou, Mengqi Gao, Feifei Zhang, Qing Wang
Summary: Rechargeable Zn-air batteries (ZABs) have attracted significant attention as high-energy density and cost-effective power sources. This study demonstrates that the performance of ZABs can be effectively improved by using the redox mediator anthraquinone-2,7-disulfonic acid disodium salt (AQDS) to enable two-electron oxygen redox chemistry. Detailed investigation of the kinetics and mechanism of the AQDS-mediated oxygen reduction reaction at different pH values reveals the reaction pathways and rate-limiting step. The AQDS-mediated Zn-air flow battery achieves considerably enhanced energy efficiency of 85% at 10 mA cm(-2) using a flow cell configuration.
ADVANCED ENERGY MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Soumyadeep Chakrabortty, Katharina Konieczny, Felix J. de Zwart, Eduard. O. Bobylev, Eszter Barath, Sergey Tin, Bernd H. Mueller, Joost N. H. Reek, Bas de Bruin, Johannes G. de Vries
Summary: Researchers achieved enantioselective hydrogenation of cyclic enamides using an earth-abundant cobalt-bisphosphine catalyst. The catalytic system, CoCl2/(S,S)-Ph-BPE, reduced trisubstituted carbocyclic enamides to saturated amides with high activity and excellent enantioselectivity (up to 99%). The methodology can be extended to the synthesis of chiral amines by base hydrolysis of the hydrogenation products. Preliminary mechanistic investigations suggested a sigma-bond-metathesis pathway for the hydrogenation of the carbon-carbon double bond, involving a high spin cobalt (II) species.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Goedele Roos, Jeremy N. Harvey
Summary: The study examines the oxidative nature of MPO and its role in the oxidation of chloride, with a focus on the significance of the sulfonium linkage and histidine in this process. Calculations on protein models reveal the influence of different ligands on the selectivity of the reaction.
JOURNAL OF PHYSICAL CHEMISTRY B
(2021)
Article
Chemistry, Applied
Akinobu Matsuzawa, Jeremy N. Harvey, Fahmi Himo
Summary: This review highlights the importance of computational studies in realizing that bimetallic complexes are the active catalytic species in some reactions, rather than monometallic complexes as previously assumed. The combination of experimental observations and computation of metal precursor speciation is a powerful tool in predicting the presence of bimetallic intermediates or transition states.
TOPICS IN CATALYSIS
(2022)
Article
Chemistry, Medicinal
Francesc Sabanes Zariquiey, Edgar Jacoby, Ann Vos, Herman W. T. van Vlijmen, Gary Tresadern, Jeremy Harvey
Summary: The combination of mixed-solvent molecular dynamics (MD) and time-structure independent component analysis (TICA) was applied to four retrospective case studies, and the results were compared with previous experimental and computational findings. It was found that the successful identification of cryptic pockets depends on the system and the cosolvent probes. The conformational state of the targets plays a critical role in docking studies with the parent ligands, which has implications for virtual screening applications.
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2022)
Article
Chemistry, Organic
Xianjun Xu, Huangdi Feng, Xiaoyong Zhang, Liangliang Song, Luc Van Meervelt, Johan Van der Eycken, Jeremy N. Harvey, Erik V. Van der Eycken
Summary: A palladium-catalyzed reaction for the synthesis of fused polycyclic indolizines has been developed. Experimental and theoretical studies suggest that the reaction involves C-C and C-O bond cleavage, providing a new approach for heterocycle synthesis.
Article
Chemistry, Physical
Xiaoyong Zhang, Pierre-Louis Lefebvre, Jeremy N. Harvey
Summary: The solvent environment has minimal influence on transition state passage dynamics of the Diels-Alder reaction in aprotic solvents, with the notable effect occurring far from the transition state region where reactants are caged within the reactant well.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Julien Escudero, Pieter Mampuys, Carl Mensch, Charles B. Bheeter, Robby Vroemans, Romano V. A. Orru, Jeremy Harvey, Bert U. W. Maes
Summary: o-Phenylene N-substituted iminocarbonates can be obtained through aerobic Ni-catalyzed reaction of readily available catechols and isocyanides. The choice of oxidant and absence of base are crucial to avoid unwanted catechol oxidation. This method is generally applicable to other oxidation-sensitive aromatic 1,2-bisnucleophiles, providing a new approach to important bicyclic heterocycles.
Article
Chemistry, Multidisciplinary
Stefan Lulf, Luxuan Guo, Tobias Parchomyk, Jeremy N. Harvey, Konrad Koszinowski
Summary: This study investigates the oxidative addition of organyl halides to phenylferrate anions in the gas phase, revealing the impact of different iron complexes on reactivity and reaction pathways. DFT calculations provide insights into the high reactivity of Ph2Fe(I)(-) complex.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Ahmed M. Rozza, Marcell Papp, Neil R. McFarlane, Jeremy N. Harvey, Julianna Olah
Summary: This study used a combination of theoretical tools to investigate various aspects of NO binding and reaction intermediates. The results suggest that NO binding leads to conformational changes in the protein.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Pablo Ramos-Sanchez, Jeremy N. Harvey, Jose A. Gamez
Summary: A novel algorithm is proposed to explore the chemical space by generating reaction networks using heuristics based on chemical theory. The algorithm improves performance by considering only transformations that break two chemical bonds and form two new ones. It estimates energy barriers using quantum chemical calculations and can also identify missed species during the previous step to further define the reaction network. The algorithm has successfully identified the most important reaction pathways in five different chemical reactions.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Physical
Andrea Daru, Carlos Martin-Fernandez, Jeremy N. Harvey
Summary: This article presents a mechanistic investigation of the iron-catalyzed Kumada reaction involving clusters as active species. It suggests that 11- and 13-coordinated clusters are fundamental for initiating the reaction, and proposes a classic initiation step.
Article
Chemistry, Physical
Tamara Rinkovec, Demian Kalebic, Mark Van der Auweraer, Wim Dehaen, Jeremy N. Harvey, Steven De Feyter
Summary: In this study, the effect of concentration on the self-assembled molecular network formation process was investigated using scanning tunneling microscopy. Isophthalic acids were chosen as a model system, and the adsorption behavior was evaluated at the nanoscale. The results showed the existence of a critical concentration for self-assembly, with the molecular structure having a significant impact on this threshold value. Furthermore, highly cooperative behavior was observed at the liquid/solid interface, providing a rare example of quantitative measurement of cooperative phenomena.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Biochemistry & Molecular Biology
Anastasia V. Lilina, Simon Leekens, Hani M. Hashim, Pieter-Jan Vermeire, Jeremy N. Harvey, Sergei V. Strelkov
Summary: Intermediate filaments (IFs) are essential components of the metazoan cytoskeleton, but their molecular architecture and assembly process are not fully understood. This study investigated the structure and stability of human vimentin, a model IF protein, and found that different regions of the protein have varying stability. These findings contribute to a better understanding of the molecular mechanisms driving IF assembly.
Article
Chemistry, Physical
Tolga Yaman, Jeremy N. N. Harvey
Summary: Novel density functional theory (DFT) calculations were performed to investigate the mechanism of a base-free Suzuki-Miyaura cross-coupling reaction with phosphine ligands. The results are consistent with experimental findings and suggest a mechanism involving recycling of the arylboronic acid moiety. Our calculations focus on the transmetalation and reductive elimination steps.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Physical
Maarten Konings, Jeremy N. Harvey, Jeïrome Loreau
Summary: In this work, Gaussian process regression machine learning representations of the three lowest coupled 2A' adiabatic electronic potential energy surfaces of the ArH2+ reactive system are presented. The nonadiabatic coupling matrix elements are also calculated. Accurate ab initio electronic structure calculations, taking into account the spin-orbit coupling, serve as input for the machine learning training process. The fitted potential energy surfaces show high accuracies, meeting the requirements for chemical dynamics at low temperature.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Tamara Rinkovec, Demian Kalebic, Mark Van der Auweraer, Wim Dehaen, Jeremy N. Harvey, Steven De Feyter
Summary: This study investigates the effect of concentration on the self-assembly process of molecular networks using scanning tunneling microscopy. The research aims to improve the understanding of 2D supramolecular chemistry by obtaining quantitative data. The results show highly cooperative behavior and the significant impact of molecular structure on the critical concentration.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
