Article
Chemistry, Applied
Yin-Feng Ma, Chuan-Jin Hou, De-Quan Wei, Xinwei He, Ting-Ting Chu, Xiu-shuai Chen, Xiang-Ping Hu
Summary: The asymmetric hydrogenation of beta-ketophosphonates with chiral Ir/P,N,N-ligands catalyst leads to high yields of beta-hydroxyphosphonates with good or excellent enantioselectivities under mild conditions.
APPLIED ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Bram B. C. Peters, Jia Zheng, Suppachai Krajangsri, Pher G. Andersson
Summary: This study reveals a novel reactivity of Crabtree-type complexes in the Ir-N,P-catalyzed hydrogenation of enones by adding benzamide and developing a reactive catalyst, resulting in a highly stereoselective reduction of enones.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Inorganic & Nuclear
Ruslan P. Shekurov, Almaz A. Zagidullin, Mikhail N. Khrizanforov, Daut R. Islamov, Tatiana P. Gerasimova, Farida F. Akhmatkhanova, Vasily A. Miluykov
Summary: In this study, racemic and enantiopure ferrocene-based P-chiral amidophosphinates were synthesized by ortho-lithiation reaction and reaction with amidochlorophenylphosphinate. The structures of the synthesized compounds were analyzed experimentally, and the oxidation and reduction reactions were observed.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Organic
Luo-Yu Wang, Jiapei Miao, Yu Zhao, Bin-Miao Yang
Summary: We report a highly selective abbreviation for the efficient synthesis of 1,1'-biheteroaryls. Under the cooperative catalysis of chiral phosphoric acid and InBr3, reactions between 2,3-diketoesters and 1,3-dione-derived enamines resulted in the highly enantioselective construction of 1,1'-pyrrole-indoles with up to 92% yield and 94% enantiomeric excess. Derivatizations of these compounds to diverse functionalized N-N linked axially chiral biheteroaryls have also been demonstrated.
Article
Chemistry, Organic
Luo-Yu Wang, Jiapei Miao, Yu Zhao, Bin-Miao Yang
Summary: We developed a highly selective method for synthesizing 1,1'-biheteroaryls bearing a chiral N-N axis. By using chiral phosphoric acid and InBr3 as cooperative catalysts, 2,3-diketoesters reacted with 1,3-dione-derived enamines to construct 1,1'-pyrrole-indoles with high enantioselectivity, up to 92% yield, and up to 94% enantiomeric excess (ee), or bisindoles with up to 92% ee. Derivatizations of these compounds resulted in diverse functionalized N-N linked axially chiral biheteroaryls.
Article
Chemistry, Organic
Rurong Yu, Feiyue Hao, Xinyu Zhang, Zhongbing Fang, Zhengneng Jin, Guyue Liu, Guoliang Dai, Jiashou Wu
Summary: A method for selectively reducing 2-pyridyl ketones and related N-heteroaryl compounds using cobalt stearate as a catalyst and DMF as a hydride source has been developed. The chelation with cobalt activates the ketone substrate, making this method highly chemoselective. A possible reaction mechanism has been proposed based on control experiments.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Yu Nie, Qianjia Yuan, Feng Gao, Masahiro Terada, Wanbin Zhang
Summary: An efficient iridium-catalyzed double asymmetric hydrogenation of 2,5-dialkylienecyclopentanones is reported, delivering chiral 2,5-disubstituted cyclopentanones in excellent yields and stereoselectivities. The results suggest that the two C=C bonds were hydrogenated in a stepwise manner and the second stereocenter was controlled by the chiral catalyst and the chirality of monohydrogenated product. The hydrogenated products can be prepared on a gram-scale and are easily derivatized.
Article
Chemistry, Organic
Yu Nie, Qianjia Yuan, Feng Gao, Masahiro Terada, Wanbin Zhang
Summary: Herein, we report an efficient iridium-catalyzed double asymmetric hydrogenation of 2,5-dialkylienecyclopentanones, delivering the chiral 2,5-disubstituted cyclopentanones in excellent yields and stereoselectivities. The results of the kinetic experiments and control experiments indicated that the two C=C bonds were hydrogenated in a stepwise manner and the second stereocenter was synergistically controlled by the chiral catalyst and the chirality of monohydrogenated product. The hydrogenated products can be prepared on a gram-scale and are easily derivatized.
Review
Chemistry, Multidisciplinary
Oleksandr Vyhivskyi, Anton Kudashev, Takeru Miyakoshi, Olivier Baudoin
Summary: Processes involving transition-metal catalysis have become a major part of synthetic chemists' toolbox in recent decades. The focus has shifted from cross-coupling reactions to C-H bond functionalization, with constant progress leading to discovery of enantioselective methods. The review discusses enantioselective Pd-0-catalyzed C-H activation, highlighting the importance of different chiral ligands and catalysts in enabling these transformations.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Zhou-Hao Zhu, Yi-Xuan Ding, Bo Wu, Yong-Gui Zhou
Summary: The asymmetric reduction of tetrasubstituted olefins has seen significant development, leading to an urgent demand for an effective method. By mimicking the coenzyme NAD(P)H, researchers have successfully reduced 2,3-substituted 1H-inden-1-ones using the catalytic chiral NAD(P)H model CYNAM, achieving high yields (up to 98%) and good enantioselectivity (up to 99% ee). The reduced product can also be efficiently used for the concise synthesis of chiral bioactive molecules.
Article
Chemistry, Multidisciplinary
Peng Lu, Hongliang Wang, Yihui Mao, Xin Hong, Zhan Lu
Summary: Investigation on asymmetric hydrogenation of olefins is vital for the synthesis of pharmaceutical molecules and chemical industry. A cobalt-catalyzed enantioconvergent hydrogenation method has been developed for common minimally functionalized E/Z-olefin mixtures.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Pier Alexandre Champagne
Summary: The first catalytic intermolecular desymmetrization of azetidines was reported in 2015, and Density Functional Theory calculations were used to uncover the mechanism and high enantioselectivity. The reaction proceeds through bifunctional activation of the azetidine nitrogen and the thione tautomer of the 2-mercaptobenzothiazole nucleophile. The selectivity is driven by the ability of the substrates to fit into the chiral catalyst pocket based on primary orbital interaction requirements.
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, Organic
Peiyuan Wang, Yaling Huang, Jierui Jing, Fen Wang, Xingwei Li
Summary: In this study, an efficient and atroposelective method for constructing C-N atropisomers was reported. By utilizing rhodium(III)-catalyzed C-H activation of sulfoxonium ylides in [4+2] annulation with sterically hindered, electron-rich alkynes, C-N axially chiral 4-functionalized 1-naphthols were synthesized with high regio- and enantioselectivity.
Article
Chemistry, Organic
Yin-Bo Wan, Xiang-Ping Hu
Summary: A readily available and highly modular class of chiral P,N,N-ligands have been developed and successfully applied in the Ir-catalyzed asymmetric hydrogenation. These ligands exhibited excellent activity, enantioselectivity, and substrate tolerance, thus providing optically active compounds with high yields and enantioselectivities. This study demonstrates the utility of these ligands in diverse product transformation and the synthesis of biologically active compounds.
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.
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, 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
Fanshi Li, Isabelle Meijer, Bauke Kniestedt, Martin Lutz, Daniel L. J. Broere, Robertus J. M. Klein Gebbink
Summary: By incorporating deuterium atoms and bulky tri-isopropyl silyl (TIPS) substituents into ligand design, the site-selective oxidation of aliphatic C-H bonds can be enhanced in non-heme iron oxidation catalysis. A series of non-heme iron complexes were developed with TIPS groups and deuterium atoms, resulting in significantly improved catalytic performance compared to counterparts without deuterium or TIPS. These bulky deuterated complexes exhibit excellent catalytic activity in oxidizing a wide range of substrates.
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, 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, 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.
