Article
Chemistry, Multidisciplinary
Sebastian Martinez-Vivas, Macarena Poyatos, Eduardo Peris
Summary: H-1 NMR studies showed that a cationic complex with a pyridine-di-imidazolylidene pincer ligand exhibited high binding affinity with coronene in CH2Cl2. This binding was established through π-stacking interactions between coronene and the planar Rh-I complex. The interaction influenced the electron-donating strength of the pincer CNC ligand and increased the reaction rate of nucleophilic attack of methyl iodide on the rhodium (I) pincer complex, as well as enhancing its catalytic activity in the cycloisomerization of 4-pentynoic acid. These findings highlight the significance of supramolecular interactions in modifying the reactivity and catalytic activity of square-planar metal complexes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Sebastian Martinez-Vivas, Dmitry G. Gusev, Macarena Poyatos, Eduardo Peris
Summary: We report a rhodium(I) complex with modulable electronic nature through supramolecular and redox stimuli. The complex shows strong pi-pi-stacking interaction with coronene, affecting its electron-richness. Addition of tetrabutylammonium fluoride sequentially reduces the ligand's NDI moiety, enhancing its electron-donor strength. The complex's catalytic activity in the cycloisomerization of alkynoic acids can be modulated by the addition of fluoride, resulting in four levels of activity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Inorganic & Nuclear
Jessica Margalef, Maria Biosca, Pol de la Cruz Sanchez, Jorge Faiges, Oscar Pamies, Montserrat Dieguez
Summary: The success of phosphine-oxazoline ligands has led to advancements in P-oxazoline ligand families, resulting in diverse structures and more efficient ligands for asymmetric transformations. Through proper design, these heterodonor bidentate ligand families exhibit superior catalytic performance in a variety of asymmetric reactions.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Pieter J. Gilissen, Xiaofei Chen, Joep De Graaf, Paul Tinnemans, Ben L. Feringa, Johannes A. A. W. Elemans, Roeland J. M. Nolte
Summary: We report a photoswitchable iron(III) salen phosphate catalyst for enantiodivergent oxidation of prochiral aryl alkyl sulfides to chiral aryl alkyl sulfoxides. The stable (S)-axial isomer of the catalyst produced enantioenriched sulfoxides with (R)-configuration up to 75% e.e., while the photoisomerized metastable (R)-axial isomer favored the formation of (S)-sulfoxides up to 43% e.e. The maximum Delta e.e. value obtained in enantiodivergent sulfoxidation was 118%, identical to that observed in the enantiodivergent epoxidation of alkenes by a related Mn1 catalyst. This iron-based catalyst expands the range of photoswitchable enantiodivergent catalysts and shows potential for development of a catalytic system capable of writing digital information on a polymer chain in the form of chiral sulfoxide functions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Xiaoxiao Xie, Sanliang Li, Qiaoyu Chen, Hao Guo, Junfeng Yang, Junliang Zhang
Summary: This article presents a novel method for the synthesis of chiral phosphorus ligands, and demonstrates their potential applications in catalytic asymmetric reactions.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Inorganic & Nuclear
David Izuchukwu Ugwu, Jeanet Conradie
Summary: The Sharpless concept of copper(I) catalyzed azide-alkyne cycloaddition reaction, also known as click chemistry, has attracted attention in the synthesis of heterocyclic molecules. However, the full potential of this simple and efficient method in the synthesis of bidentate ligands for coordination chemistry has not been fully explored. This review focuses on the advancements in the application of click chemistry in the synthesis of bidentate ligands and the utilization of the metal complexes derived from these ligands in catalysis.
Article
Chemistry, Multidisciplinary
Yang-Ming Zhang, Shu-Min Guo, Qing-Xian Wang, Xiao-Jie Zheng, Jian-Hua Xie, Qi-Lin Zhou
Summary: This paper reports the design and synthesis of spirochroman-2-on-4,1'-indan-7'-ol (SCIOL) and its application for synthesizing chiral monophosphinite ligands. The synthesis process involves a tandem double Friedel-Crafts reaction/lactonization to construct the spiro framework, and the desired racemic SCIOL was obtained via 6 steps with a total yield of 44.5%. Optical SCIOL was obtained in good yields on a gram scale using an inclusion resolution with N-benzylcinchonidinium chloride. Preliminary studies showed that the corresponding chiral spiro monophosphinite ligands exhibit high catalytic activity and enantioselectivity (up to 94% ee) in the rhodium-catalyzed asymmetric hydrogenation of N-acetyl dehydroamino esters. These findings highlight the significant potential of SCIOL as a useful framework for the development of chiral spiro ligands.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Jesus de Maria Perez, Mateo Alajarin, Alberto Martinez-Cuezva, Jose Berna
Summary: The catalytic activity of degenerate succinamide-based [2]rotaxanes can be modulated by changes at their macrocyclic component. The variation in catalytic efficiency is correlated with the electronics and dynamics of the entwined macrocycle.
ORGANIC CHEMISTRY FRONTIERS
(2022)
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, Organic
Guang-Da Xia, Zi-Kui Liu, Yu-Lian Zhao, Feng-Cheng Jia, Xiao-Qiang Hu
Summary: The synthesis of tertiary phosphines(III) has been a long-standing challenge in synthetic chemistry due to issues including harsh conditions, sensitive organometallic reagents, and pre-functionalized substrates. In this study, a strategically novel C(sp(3))-H bond phosphorylation method is reported, which allows for the synthesis of structurally diverse tertiary phosphines(III) from industrial phosphine(III) sources under mild photocatalytic conditions. The combination of ligand-to-metal charge transfer (LMCT) and hydrogen atom-transfer (HAT) process enables the generation of alkyl radicals from hydrocarbons. Furthermore, this catalytic system can also be applied for the polymerization of electron-deficient alkenes.
Article
Chemistry, Inorganic & Nuclear
Sanjay Gaire, Briana R. Schrage, Christopher J. Ziegler
Summary: It has been shown that an organometallic complex mimicking an amino acid can be synthesized, and by adjusting the structure of the metal species, compounds with different chirality can be produced.
INORGANIC CHEMISTRY
(2021)
Review
Chemistry, Inorganic & Nuclear
Zeyneb Kaya, Embarek Bentouhami, Katrin Pelzer, Dominique Armspach
Summary: Cavity-shaped ligands can act as containers for metal centers, influencing the coordination sphere of metals, particularly in asymmetric metal catalysis. The spatial control around the coordinated substrate is crucial for achieving high ee values in asymmetric metal-catalyzed reactions. Various approaches, both covalent and supramolecular, have been used to achieve enantiodiscrimination in these reactions by metal complexation within or near chiral capsular environments.
COORDINATION CHEMISTRY REVIEWS
(2021)
Review
Chemistry, Inorganic & Nuclear
Helene Pellissier
Summary: This review summarizes the recent developments in the use of TADDOL-derived phosphorus ligands in asymmetric metal catalysis, demonstrating their effectiveness in promoting various highly enantioselective transformations with different metals. (c) 2023 Elsevier B.V. All rights reserved.
COORDINATION CHEMISTRY REVIEWS
(2023)
Article
Chemistry, Inorganic & Nuclear
Suguru Sakai, Kazuya Kanemoto, Shin-ichi Fukuzawa
Summary: In this study, a novel planar chiral phosphine ligand was developed and prepared through a series of steps. It showed good catalytic activity in Suzuki-Miyaura coupling reactions and moderate enantioselectivity in asymmetric reactions using optically active versions.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Review
Chemistry, Applied
Thomas Schlatzer, Rolf Breinbauer
Summary: Transition metal-catalyzed reactions in aqueous media are gaining increasing interest due to advantages in cost, safety, and versatility. These reactions are used in homogenous catalysis, life sciences, and biocatalysis, utilizing water-soluble phosphine ligands for reliable catalysis in the aqueous phase. Recent advancements in synthetic strategies for hydrophilic phosphines and phosphites, as well as their applications in transition metal catalysis using aqueous solvents, are summarized in this review.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
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.
Review
Chemistry, Multidisciplinary
Rens Ham, C. Jasslie Nielsen, Sonja Pullen, Joost N. H. Reek
Summary: Because sunlight is abundant and can generate excited states, it has great potential for practical applications in sustainable energy supply and organic synthesis. Photosensitizers and supramolecular coordination cages play crucial roles in harnessing light energy and facilitating close proximity of different components for photocatalysis. This review focuses on the application of supramolecular cages in artificial photosynthesis, organic photo(redox) catalysis, and provides inspiration for the future design of photocatalytic supramolecular host-guest systems.
Article
Chemistry, Multidisciplinary
Bin Sun, Eva J. J. Meeus, Felix J. J. de Zwart, Eduard O. O. Bobylev, Tiddo J. J. Mooibroek, Simon Mathew, Joost N. H. Reek
Summary: Coordination chemistry is a powerful method for synthesizing supramolecular cages with specific applications. This study successfully synthesized discrete, homochiral (Fe2L3)-L-II cages through chirality-driven self-assembly. The size of these cages can be controlled by stereochemical manipulation of the iron(II) centers, and their formation requires chirality at both the vertices and ligand backbones. The smaller cages exhibit stereoselectivity with only chiral ligands, and their formation is driven by non-covalent interactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
C. Jasslie Nielsen, Petrus C. M. Laan, Raoul Plessius, Joost N. H. Reek, Jarl Ivar van der Vlugt, Sonja Pullen
Summary: Photoredox catalysis is a valuable tool in various chemical reactions, but it faces challenges such as photodegradation of photocatalysts and substrates, short lifetimes of reactive intermediates, and selectivity issues due to unwanted side reactions. One potential solution is the pre-organization of photosensitizers, substrates, and (co)-catalysts in supramolecular self-assembled structures, which can stabilize dyes and improve selectivity through non-covalent interactions.
FARADAY DISCUSSIONS
(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, Physical
Catriona C. James, Petrus C. M. Laan, Bas de Bruin, Joost N. H. Reek
Summary: Olefin metathesis catalysts, such as AquaMet, are susceptible to decomposition under biologically relevant conditions. Current stabilizing strategies have limited applicability under these conditions. Encapsulation of AquaMet within a supramolecular metallocage, with nitrate counterions, enhances the catalyst activity. Replacement of AquaMet's chloride ligands with nitrates through simple anion-exchange leads to higher yields of ring-closed product under aqueous and biological conditions. This kinetic protection strategy of transition metal catalysts may find applications in other in vivo catalytic reactions.
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
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, Physical
Pim R. Linnebank, David A. Poole, Alexander M. Kluwer, Joost N. H. Reek
Summary: The use of data driven tools to predict the selectivity of homogeneous catalysts has been studied, but the use of substrate descriptors to rationalize the catalytic outcome is relatively unexplored. In this study, the regioselectivity of the hydroformylation reaction of terminal alkenes was predicted with high accuracy using the ?C-13 NMR shift and I-CC stretch descriptors for a non-encapsulated rhodium based catalyst. However, the use of substrate descriptors for an encapsulated catalyst appeared more challenging.
FARADAY DISCUSSIONS
(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, Renzo A. Knol, Simon Mathew, I. I. I. David A. Poole, Ioli Kotsogianni, Nathaniel I. Martin, Bas de Bruin, Alexander Kros, Joost N. H. Reek
Summary: There is a growing interest in using metal-organic cages (MOCs) in the field of biomedicine due to their unique distribution in organisms and novel cytotoxicity mechanisms. However, the stability of many MOCs under in vivo conditions hinders their study in living cells. In this study, the toxicity and photophysical properties of stable rhodamine-functionalized platinum-based Pt2L4 nanospheres and their building blocks are investigated in vitro and in vivo. The results show that the Pt2L4 nanospheres exhibit reduced cytotoxicity and altered biodistribution compared to the building blocks in zebrafish and human cancer cell lines. These findings provide a basis for the application of MOCs in cancer therapy.
Article
Chemistry, Multidisciplinary
Eva J. Meeus, Nico V. Igareta, Iori Morita, Thomas R. Ward, Bas de Bruin, Joost N. H. Reek
Summary: This study demonstrates that the incorporation of a biotinylated Co(TAML) cofactor within streptavidin enhances the activity and enantioselectivity of asymmetric radical-type oxygen atom transfer catalysis.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Dimitris I. Ioannou, Luca Capaldo, Jiri Sanramat, Joost N. H. Reek, Timothy Noel
Summary: Electrophotocatalysis plays a significant role in organic synthesis and has potential for scalability. This study introduces a new concept of a flow reactor that utilizes both photons and electrons simultaneously. The device is not only applicable for electrophotocatalysis, but also for purely electrochemical and photochemical reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
