Article
Chemistry, Physical
Zhiqian Yu, Qianhui Liu, Yudong Yang, Jingsong You
Summary: This study demonstrates that phenolic compounds can serve as effective ligands to control the regioselectivity of ortho-C-H arylation reactions, enabling the synthesis of various biaryl phosphines in a streamlined and practical manner. The phosphine ligand library shows great potential in catalytic coupling reactions and exhibits unique chemoselectivity when compared with commercially available classic phosphine ligands.
Article
Chemistry, Multidisciplinary
Xiaoqiang Yan, Jijun Jiang, Jun Wang
Summary: In this study, an unusual class of planar-chiral rhodium catalysts bearing non-chiral Cp ligands was described. These catalysts are readily tunable and were successfully used in enantioselective C-H activation reactions, showing great potential in this field.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Xavier Marset, Marti Recort-Fornals, Malkaye Kpante, Adam Zielinski, Christopher Golz, Lawrence M. Wolf, Manuel Alcarazo
Summary: A series of strong it-acceptor polyfluorinated and dicationic chelating phosphines were synthesized and evaluated in the Rh-catalysed dimerization of norbornadiene, leading to the selective formation of specific products and site-selective arylation reactions. Theoretical calculations were performed to understand the origin of the observed regioselectivity.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Takanobu Saito, Joaquim Caner, Naoyuki Toriumi, Nobuharu Iwasawa
Summary: A novel method for the meta-selective C-H carboxylation of 1,1-diarylethylene derivatives using a rhodium catalyst and a stoichiometric reductant has been achieved. The introduction of a carboxyl group to the aryl ring at the meta-position was enabled with high selectivity. Both experimental and computational mechanistic studies indicate that a specific rhodium migration process plays a key role in this unusual aryl-to-aryl 1,2-rhodium shift.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Jinyuan Jiang, Jidan Liu, Zhenke Yang, Liyao Zheng, Zhao-Qing Liu
Summary: A one-pot three-component synthesis of benzofuran-3(2H)-ones with tetrasubstituted carbon stereocenters has been successfully developed via Rh(III)-catalyzed C-H/C-C bond activation and cascade annulation, using salicylaldehydes, cyclopropanols, and alkyl alcohols as starting materials.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Xiang-Ting Min, Ding-Wei Ji, Yu-Qing Guan, Shi-Yu Guo, Yan-Cheng Hu, Boshun Wan, Qing-An Chen
Summary: Transition metal catalyzed decarbonylation offers a unique synthetic strategy for new chemical bond formation. The study developed a visible light induced rhodium catalysis for decarbonylative coupling of imides with alkynes under ambient conditions, revealing the rhodium complex serves as both the catalytic center and photosensitizer. This visible light promoted catalytic decarbonylation strategy opens up new opportunities for re-evaluating old transformations with ligand dissociation as a rate-determining step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Liselle Atkin, Daniel L. Priebbenow
Summary: Investigations revealed that the indenyl-derived catalyst significantly accelerated the directed ortho C-H amidation of benzoyl silanes using 1,4,2-dioxazol-5-ones. The slippage of the indenyl complex enables ligand substitution at the metal center to proceed via associative pathways, leading to rate and yield enhancements. Interestingly, this phenomenon is specific for weakly coordinating carbonyl-based directing groups, with no acceleration observed for nitrogen-based directing groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Bartlomiej Sadowski, Binbin Yuan, Zhipeng Lin, Lutz Ackermann
Summary: In this study, electrocatalytic peri C-H alkenylation of 1-naphthols was achieved using rhodium(III) catalysis under constant current electrolysis conditions. This strategy offers a wide scope, good functional group tolerance, and high site- and stereoselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Xuefeng Tan, Leonardo Massignan, Xiaoyan Hou, Johanna Frey, Joao C. A. Oliveira, Masoom Nasiha Hussain, Lutz Ackermann
Summary: The rhodium bimetallic electrocatalytic system enables arene C-H oxygenation by weakly coordinating amides and ketones, leading to selective dihydrooxazinone synthesis through twofold C-H functionalization. Mechanistic studies using experiment, mass spectroscopy, and cyclovoltammetric analysis support an unprecedented electrooxidation-induced C-H activation in the bimetallic rhodium catalysis manifold.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Shrikant M. Khake, Naoto Chatani
Summary: The Rh(III)-catalyzed reaction of aniline derivatives containing a pyrimidine directing group with vinylsilanes leads to the formation of C3-substituted indoline derivatives via a highly regioselective C-H activation/alkene cyclization cascade. Mechanistic experiments suggest that C-H bond cleavage is not the rate-determining step, but rather the reaction proceeds through the formation of a six-membered rhodacycle as a key catalytic species via pyrimidine-directed electrophilic ortho-C-H rhodation.
Article
Chemistry, Physical
Manikantha Maraswami, Thomas Diggins, Jeffrey Goh, Raymond Tio, Wan Qing Renee Ong, Hajime Hirao, Teck-Peng Loh
Summary: This study presents a highly selective synthesis method for indene or 1-naphthol derivatives through intramolecular alkene-alkene cross-coupling, which works with different alkene pairs to give products in good to satisfactory yields. The indene products of the reaction allow further derivatization, and the reaction pathway is dependent on alkene functionalities.
Article
Chemistry, Physical
Charles B. Musgrave, Weihao Zhu, Nathan Coutard, Jeffrey F. Ellena, Diane A. Dickie, T. Brent Gunnoe, William A. Goddard
Summary: In this study, we investigated the mechanism of oxidative conversion of benzene and ethylene to styrene using Cu(II) and Rh-Cu-Rh active catalyst. The incorporation of Cu(II) into the active Rh-Cu-Rh catalyst reduced the activation barrier for benzene C-H activation, O-H reductive elimination, and ethylene insertion into the Rh-Ph bond.
Article
Chemistry, Organic
Mahadev Sharanappa Sherikar, Ravi Devarajappa, Kandikere Ramaiah Prabhu
Summary: The annulation of primary and secondary benzamide and cinnamamide derivatives using allyl alcohol as a coupling partner catalyzed by Rh(III) involves a dual role of Rh(III) as an oxidant and a catalyst for C-H activation. Mechanistic studies reveal the involvement of AgSbF6 in halide scavenging and cyclization reactions to form desired lactams, providing a useful method for synthesizing biologically active compounds.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Qiang-Qiang Li, Yosuke Hamamoto, Cheryl Cai Hui Tan, Hiroyasu Sato, Shingo Ito
Summary: A new synthetic approach to pi-extended imidazolium salts has been developed, which involves the 1,3-dipolar cycloaddition of polycyclic aromatic azomethine ylides with imidoyl chlorides. The addition of cesium fluoride as an additive is crucial for the successful conversion. Experimental and theoretical studies show that this cycloaddition proceeds via a stepwise mechanism. This method provides an efficient way to synthesize various imidazolium-containing polycyclic aromatic compounds.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Applied
Liming Zhang, Ru Zhao, Chunhui Liu, Zhaoyang Li, Jun-Long Niu, Hao-Ran Yang, Lijun Gao, Shuang-Liang Liu, Liming Zhou
Summary: The Rh(III)-catalyzed ortho alkylation of N-pyridylcarbazoles with nitroalkenes has been developed for the synthesis of a wide range of 2-(2nitroalkyl)carbazoles. Aromatic and aliphatic nitroalkenes both successfully participated in this alkylation reaction. The protocol also worked well with an indoline based substrate. Derivatization of the representative nitroalkane product was described.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Giulia Giubertoni, Gijs Rombouts, Federico Caporaletti, Antoine Deblais, Rianne van Diest, Joost N. H. Reek, Daniel Bonn, Sander Woutersen
Summary: Inspired by NMR, IR-DOSY is a technique that characterizes both molecular structure and size using infrared spectroscopy. It achieves sensitivity to the diffusion coefficient by creating a concentration gradient and tracking its equilibration. Molecules with different sizes are separated into distinct sets of IR peaks in the IR-DOSY spectrum. The 3D-IR-DOSY combines conformation sensitivity with size sensitivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
T. Bouwens, T. M. A. Bakker, K. Zhu, J. Hasenack, M. Dieperink, A. M. Brouwer, A. Huijser, S. Mathew, J. N. H. Reek
Summary: Inspired by natural photosynthesis, we use supramolecular machinery to inhibit electron-hole recombination in molecular photoelectrochemical devices, resulting in an increase in power conversion efficiency.
Article
Chemistry, Multidisciplinary
Minghui Zhou, Simon Mathew, Bas de Bruin
Summary: A new T-type molecular photoswitch based on the reversible cyclization of 1H-2-benzo[c]oxocins has been developed. The switching mechanism involves light-triggered ring contraction and thermal ring-opening processes. The new molecular-switching platform exhibits independence from solvent polarity and is suitable for biological applications. The reactions proceed with good efficiency and can be easily adjusted via structural functionalization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
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)
Review
Chemistry, Multidisciplinary
Catriona C. James, Bas de Bruin, Joost N. H. Reek
Summary: The importance of transition metal catalysis lies in its wide range of applications, including the synthesis of chemicals, natural products, and pharmaceuticals. However, a relatively new application is the catalysis of new-to-nature reactions inside living cells. The complex environment of living cells poses challenges to transition metal catalysts due to the potential inhibition or deactivation by various biological components. In this review, we summarize the current progress in the field of transition metal catalysis, focusing on the evaluation of catalysis efficiency under living cell and biological conditions. Catalyst poisoning is a common issue in this field, and we suggest that future research should explore physical and kinetic protection strategies to enhance the reactivity of catalysts in cells.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Eduard O. O. Bobylev, Julian Ruijter, David A. I. I. I. A. Poole, Simon Mathew, Bas de Bruin, Joost N. H. Reek
Summary: Inspired by catalytic regulation in living cells, we developed a Pt2L4 cage whose activity can be controlled by binding effector molecules. The cage shows catalytic activity in the lactonization reaction, with the rate depending on the bound effector guest. Some effector guests enhance the rate by up to 19-fold, while one decreases it by 5-fold. When specific substrate mixtures are used, both starting materials and products act as guests, enhancing catalytic activity for one substrate and reducing it for the other. The addition of effector molecules enables the development of more complex, metabolic-like catalyst systems.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Demi D. Snabilie, Eva J. Meeus, Roel F. J. Epping, Zhiyuan He, Minghui Zhou, Bas de Bruin
Summary: Transition metal radical-type carbene transfer catalysis is a sustainable and atom-efficient method for C-C bond formation. Understanding off-cycle and deactivation pathways can lead to solutions for avoiding catalyst deactivation and reveal novel reactivity for new applications, stimulating further development of radical-type carbene transfer reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
David A. Poole III, Eduard O. Bobylev, Bas de Bruin, Simon Mathew, Joost N. H. Reek
Summary: This article investigates the self-assembly of spherical three-dimensional (3D) cages composed of palladium(II) and pyridyl ligands. The self-assembly process is found to be sensitive to the solvents, reagents, and/or reactants used, which hinders the development of desired palladium-based cages. The study reveals that ligand substitution can be facilitated by endogenous supporting ligands derived from the solvents, reagents, and reactants.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Roel F. J. Epping, David Vesseur, Minghui Zhou, Bas de Bruin
Summary: Discovered in the 1970s as organometallic curiosities, carbene radicals have become essential in modern homogeneous catalysis. These radicals exhibit nucleophilic reactivity different from electrophilic Fischer carbenes. The successful catalytic application of carbene radicals has led to the synthesis of diverse carbon and heterocyclic compounds. This Perspective provides an overview of the coordination chemistry, reactivity, and catalytic application of carbene radicals using transition metal complexes and catalysts since 2011.
Article
Chemistry, Physical
Petrus C. M. Laan, Felix J. de Zwart, Emma M. Wilson, Alessandro Troglia, Olivier C. M. Lugier, Norbert J. Geels, Roland Bliem, Joost N. H. Reek, Bas de Bruin, Gadi Rothenberg, Ning Yan
Summary: In this study, the reactivity and selectivity of two forms of NiOOH (beta-NiOOH and gamma-NiOOH) were examined using three typical alcohols as model reactions. The results showed that the solvent had an effect on the reaction rate of beta-NiOOH but not on its selectivity. Moreover, high concentrations of OH(-) in aqueous solvent promoted the conversion of benzyl alcohol to benzoic acid. The mechanism of oxidative dehydrogenation of benzyl alcohol to benzaldehyde was also elucidated. This work highlights the unique oxidative and catalytic properties of NiOOH in alcohol oxidation reactions and contributes to the mechanistic understanding of electrochemical alcohol conversion using NiOOH-based electrodes.
Article
Chemistry, Multidisciplinary
Petrus C. M. Laan, Eduard O. Bobylev, Felix J. de Zwart, Joppe A. Vleer, Alessandro Troglia, Roland Bliem, Gadi Rothenberg, Joost N. H. Reek, Ning Yan
Summary: Controlling the coordination sphere of heterogeneous single-metal-site catalysts is a difficult task, but immobilizing supramolecular cages to control the ligand design of the primary- and secondary coordination spheres allows for fine-tuning of catalytic properties. The study of the hydrolysis of ammonia borane revealed that placing a well-defined reaction pocket around the active site can enhance catalytic performance, resulting in diffusion-controlled reaction kinetics.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Subrata Das, Andreas W. Ehlers, Sima Patra, Bas de Bruin, Buddhadeb Chattopadhyay
Summary: A concept for intermolecular C-N cross-coupling amination has been discovered using tetrazoles and aromatic and aliphatic azides with boronic acids under iron-catalyzed conditions. The reaction follows an unprecedented metalloradical activation mechanism, different from traditional metal-catalyzed C-N cross-coupling reactions. The wide scope of this reaction has been demonstrated by employing various tetrazoles, azides, and boronic acids. Moreover, the reaction has shown potential for applications in medicinal chemistry, drug discovery, and pharmaceutical industries, as demonstrated by late-stage aminations and synthesis of a drug candidate.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Jianghua Liu, Eduard O. Bobylev, Bas de Bruin, Joost N. H. Reek
Summary: This article reports on a gold catalyst based on azobenzene-bearing N-heterocyclic carbene, whose reactivity in a cyclization reaction is dependent on the isomeric state of the azobenzene. The configurations of the catalyst can be reversibly switched by light and remain stable during the reaction, effectively leading to a switchable catalyst system.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Eduard. O. Bobylev, Leonardo Passerini, Felix J. de Zwart, David A. Poole, Simon Mathew, Martina Huber, Bas de Bruin, Joost N. H. Reek
Summary: In this study, a post-assembly modification approach is described to selectively coordinate transition metals in Pd12L24 cuboctahedra. The method involves the preparation of Pd12L24 nanospheres with protonated nitrogen donor ligands that are covalently linked at the interior. Selective formation of different coordination forms of the transition metals is achieved by using different nitrogen donor ligands. Experimental and computational investigations support the presence of complexes at precise locations in the nanospheres.
Article
Chemistry, Multidisciplinary
Meiling Xu, Bin Sun, David A. Poole III, Eduard O. Bobylev, Xu Jing, Jinguo Wu, Cheng He, Chunying Duan, Joost N. H. Reek
Summary: This study reports an example of supramolecular cages with fixed gold complexes at the windows, showing confinement effects, stability, and enzymatic catalytic characteristics in gold-catalyzed reactions.