Article
Chemistry, Organic
Jihui Gao, Jie Ni, Rongrong Yu, Gui-Juan Cheng, Xianjie Fang
Summary: This highly regioselective nickel-based catalyst system enables the isomerization/hydrocyanation of aliphatic internal olefins, providing a variety of aliphatic nitriles with excellent regioselectivities and good yields under mild conditions. The reaction protocol, under Lewis acid-free conditions, shows broad functional group tolerance, including secondary amine and unprotected alcohol groups.
Review
Chemistry, Organic
Fang Zhao, Wenjing Ye, Kai Wang
Summary: The study of chiral monophosphorous ligands, especially chiral mono-phosphites ligands and mono-phosphoramidites ligands, has attracted widespread attention since the 21st century. These ligands are widely used in various asymmetric catalytic reactions for their ease of synthesis and excellent stability, activity, and enantioselectivity. The diverse common monodentate phosphonites, phosphites, and phosphoramidites ligands and their applications in asymmetric hydrogenations have made significant progress over the past two decades.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(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)
Review
Chemistry, Organic
Changjiang Li, Zhaozhou Li, Kunpeng Tan, Guodu Liu
Summary: Rhodium-catalyzed hydroformylation of olefins is a significant method for synthesizing aldehydes, and the regioselectivity and enantioselectivity of the product controlled by ligands are commonly used strategies. The modular synthesis of phosphite and phosphoramidite ligands has advantages of simple synthesis and high catalytic activity, thus being widely used in hydroformylation reactions. This review focuses on the synthesis methods and design ideas of such ligands, as well as their application effects in hydroformylation reactions, aiming to provide a reference for ligand design and synthesis in subsequent hydroformylation.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Organic
Chenga Luo, Yanli Yin, Zhiyong Jiang
Summary: Enantioenriched organophosphates play important roles in chiral ligands, catalysts, and bioactive molecules. Synthetic chemists have made significant efforts to develop efficient methodologies for constructing P-chiral phosphine derivatives, leading to a wide range of chiral organophosphine ligands and promising pharmaceutical molecules. This review summarizes and discusses the progress in the synthesis of P-chiral phosphine oxides from 2020 to 2022, focusing on asymmetric induction, catalytic desymmetrization, catalytic asymmetric synthesis, catalytic kinetic resolution or dynamic kinetic asymmetric transformation, and enzyme catalysis.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Peng Gao, Guanfeng Liang, Tong Ru, Xiaoyan Liu, Haifeng Qi, Aiqin Wang, Fen-Er Chen
Summary: Single-atom Rh catalysts show superior activity in olefins hydroformylation but limited success in regioselectivity control. By developing a Rh1 single-atom catalyst with nanodiamond as support, the catalyst achieved good to excellent regioselectivities in hydroformylation of arylethylenes, comparable to homogeneous counterparts. The coordination interaction between Rh-1 and surface phosphorus species was clarified by P-31 solid-state NMR and X-ray absorption spectroscopy.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Mate M. Major, Szabolcs Balogh, Jozsef Simon, Jozsef Bakos, Gergely Farkas
Summary: Thioether-phosphite ligands with axially chiral moiety were synthesized and their [Rh(COD)(SP)]BF4 complexes showed selective dynamics in NMR studies. Bis-ligated thioether-phosphite Rh-complexes can efficiently catalyze asymmetric hydrogenation reactions due to their distinct coordination chemistry, as confirmed by in situ NMR studies. Unlike phosphine-phosphite complexes, they form two types of bis-ligated species at higher ligand-to-metal ratio.
JOURNAL OF COORDINATION CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Pol de la Cruz-Sanchez, Maria Biosca, Marc Magre, Jorge Faiges, Jessica Margalef, Oscar Pamies, Montserrat Dieguez
Summary: High enantioselectivities and activities were achieved in the Pd-catalyzed allylic substitution reaction using a family of adaptable ligands. The ligands demonstrated high performance in various catalytic processes.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Felix Bauer, Niklas Dierenbach, Bernhard Breit
Summary: Here, an improved self-assembling phosphorus ligand based on hydrogen bonding between pyridone/hydroxypyridine in the ligand backbone is reported. The N-pyrrolyl substituents significantly enhance the pi-backbonding properties of the ligand. Rhodium, iridium, and platinum complexes of the ligand were synthesized and characterized using NMR spectroscopy and x-ray crystal structure analysis. The ligand-based catalyst exhibited high catalytic activity and linear regioselectivity in rhodium-catalyzed hydroformylation of 1-octene, as well as in linear regioselective iridium-catalyzed hydroformylation of 1-octene.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Long-Fei Nan, Xiu-Shuai Chen, Hao Chen, Xin-Hu Hu, Xin-Hong Wang, Xiang-Ping Hu
Summary: Unsymmetrical hybrid chiral diphosphorus ligands have been developed and successfully applied in iridium-catalyzed asymmetric hydrogenation of imines, leading to the synthesis of optically active amines with high yields and excellent enantioselectivities.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Ming Cui, Zhi-Yuan Zhao, Martin Oestreich
Summary: Chiral bis(phosphine) monooxides derived from C-2-symmetric bis(phosphines) have been found to exhibit superior enantioselection in copper-catalyzed conjugate borylation and 1,6-addition reactions. Specifically, (R,R)-Bozphos ligand shows significantly higher enantiomeric excesses and chemical yields compared to parent (R,R)-Me-Duphos ligand.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Chenfei Yao, Wenjie Xiong, Haining Sun, Chenzhou Li, Youting Wu, Zhibing Zhang, Xingbang Hu
Summary: In this study, a series of phosphine ligands were used to coordinate with iridium to find a cheaper and effective alternative to expensive rhodium-based catalysts for the hydroformylation of propene. Tripyridyl phosphine iridium Ir-2(cod)(2)Cl-2-P(3-py)(3) (Ir(i)-L5) and its derivatives showed the highest catalytic reactivity, surpassing that of Rh-2(cod)(2)Cl-2-P(3-py)(3) (Rh(i)-L5). The Ir(i)-L5 complex exhibited higher turnover number (TON) values when reactions were performed in polar solvents, and different n-butyraldehyde/iso-butyraldehyde (n/i) ratios can be obtained by adjusting the phosphine ligands or gas pressure proportions. The catalyst also demonstrated good reusability and a probable reaction mechanism was proposed based on DFT theoretical calculations.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Ying Ding, Jinguo Long, Xianjie Fang
Summary: A nickel-catalyzed hydrocyanation of aliphatic allenes with excellent regioselectivity has been developed. This protocol features mild reaction conditions and good functional group tolerance, providing an efficient catalytic pathway to access various allylic nitriles containing quaternary carbon centers in a one-step fashion. Additionally, preliminary attempts were made to investigate an asymmetric version of this reaction.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Chun Qian, Qingshu Zheng, Jie Chen, Bo Tu, Tao Tu
Summary: Solid main-chain NHC-rhodium(i) polymers prepared by coordination assembly show high catalytic activity in the hydroaminomethylation of olefins, with significantly improved yields and linear selectivity. The catalyst also exhibits broad substrate scope and excellent recyclability, making it suitable for the synthesis of various pharmaceuticals.
Article
Chemistry, Applied
Max N. Kliemann, Simon Teeuwen, Christopher Weike, Giancarlo Francio, Walter Leitner
Summary: The catalytic asymmetric hydroformylation of styrenes was combined with condensation of the resulting aldehydes with acetohydrazide as nucleophile, producing gamma-chiral N'-substituted acetohydrazones. This cascade reaction, called hydrohydrazonemethylation (HHM), was achieved using a commercially available chiral phosphine-ligand and [Rh(acac)(CO)(2)] as catalysts. The stable condensation products provided versatile chiral intermediates, which can be further reduced to obtain gamma-chiral N'-substituted acetohydrazides and beta-chiral hydrazines.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
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, Organic
Joss Pepe Strache, Lukas Muenzer, Andreas Adler, Dirk Blunk, Hans-Guenther Schmalz
Summary: We investigated the enantioselective Ni-catalyzed hydrocyanation of 1,3-diarylpropenes. A series of (E)-homostilbenes were prepared by Pd-catalyzed coupling, and the hydrocyanation of various homostilbenes was studied using a Ni(cod)2/TADDOL-derived chiral phosphine-phosphite ligand catalyst system. The methodology was applied in a short synthesis of a colchicine analogue, and the absolute configuration of 2,4-diphenylbutyronitrile was determined by comparing experimental and calculated ECD spectra.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Lars Hemmersbach, Ruth Adam, Christina Plevnali, Xinmiao Zhang, Benito Yard, Hans-Gunther Schmalz
Summary: A new anti-inflammatory agent, which releases carbon monoxide (CO) and a specialized pro-resolving mediator, was successfully synthesized. It can induce HO-1 expression in endothelial cells and M2 polarized macrophages, but its role in inflammation resolution still needs to be assessed.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Polymer Science
Lazaros Papadopoulos, Natalia Maria Malitowski, Dimitrios Bikiaris, Tobias Robert
Summary: A series of bio-based polyesters derived from itaconic acid were synthesized as alternative binder resins for UV-curing additive manufacturing processes. These polyesters, created using different diols and dicarboxylic acids from petrochemical and renewable resources, have not been previously described. The influence of the chemical structures of these materials on their physicochemical properties was thoroughly investigated. The polyesters showed tunable properties and an overall bio-based content up to 85%, making them suitable for additive manufacturing materials.
EUROPEAN POLYMER JOURNAL
(2023)
Article
Biochemistry & Molecular Biology
Lea Hartmann, Florian P. Seebeck, Hans-Guenther Schmalz, Dirk Gruendemann
Summary: Recently, a non-enzymatic multi-step cycle for the regeneration of ergothioneine (ET) has been discovered after reaction with singlet oxygen (1O2) by glutathione (GSH). Through experiments using labeled ET and high resolution mass spectrometry analysis, the reaction scheme has been revised and extended, with 1O2 attacking the imidazole ring and the sulfur of ET. The reduction of the hydroperoxide intermediates and the sulfine allows for the complete regeneration of ET by GSH, without the need for enzyme involvement.
FREE RADICAL BIOLOGY AND MEDICINE
(2023)
Article
Chemistry, Multidisciplinary
Reinhold Gregor Wuestenberg, Joerg-Martin Neudoerfl, Hans-Guenther Schmalz
Summary: Using the marine natural product ptilocaulin as a starting point, the study investigated the supramolecular behavior of N,N'-bridged guanidinium nitrates in crystalline state. Various N,N'-bridged guanidines were synthesized and converted into nitrate salts, and their crystal structures were determined. The study identified several recurring supramolecular motifs formed by charge-assisted self-assembly and revealed the value of N,N'-bridged guanidines as building blocks for supramolecular chemistry and crystal engineering.
ISRAEL JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Lukas Muenzer, Hans-Guenther Schmalz
Summary: In this paper, the results and experience gained from 20 years of research in the field of polyketidic natural products with a tetra-ortho-substituted benzophenone substructure are summarized. Despite the challenges posed by the intense interactions of the functional groups adjacent to the ketone bridge, the synthesis of such systems is important for understanding the non-enzymatic formation of related compounds in Nature. Successes, failures, and surprising reactivities are reported based on the approaches used to target Mumbaistatin and Pestalone, both of which are of high biological relevance.
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, Organic
Dominik Albat, Slim Chiha, Stephan Dohmen, Pascal M. Engelhardt, Hanna Sebode, Arne Soicke, Matthias Barone, Matthias Mueller, Ronald Kuehne, Hans-Guenther Schmalz
Summary: In this study, we describe the modular assembly of ProM-based pentapeptidic EVH1 ligands through liquid phase peptide synthesis, which allows for facile alteration of the C-terminal ProM unit and improved overall yields and purity.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Lazaros Papadopoulos, Natalia Maria Malitowski, Alexandra Zamboulis, Stefan Friebel, Dimitrios Bikiaris, Tobias Robert
Summary: Two sets of polyesters were prepared from hexanediol, succinic acid, and a second aromatic dicarboxylic acid. Isophthalic acid was used as a rigid building block in the first set, while it was replaced by the bio-based 2,5-furandicarboxylic acid in the second set. The polyesters' structure and properties were characterized, and they were used as polyols to synthesize water-borne polyurethane dispersions. Films made from the dispersions showed that the bio-based acid had similar or even superior effects on the thermal and mechanical properties of the coatings compared to the fossil-based counterpart.
REACTIVE & FUNCTIONAL POLYMERS
(2023)
Article
Chemistry, Multidisciplinary
Lazaros Papadopoulos, Lorenzo Pezzana, Natalia Maria Malitowski, Marco Sangermano, Dimitrios. N. N. Bikiaris, Tobias Robert
Summary: In the search for sustainable thermosets, research has been conducted on various polymer classes, including epoxy, benzoxazines, acryl-/methacrylates, etc. Itaconic acid-based unsaturated polyester resins are a particular group that can also be used as sustainable inks for additive manufacturing. This study synthesized a series of itaconic acid-based polyesters with different reactive diluent contents and evaluated their physicochemical properties and reactivity toward UV light. The same formulations were used for 3D printing and their thermomechanical properties were examined.
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: In this study, a supramolecular cage with an extended catalytic region from the cavity to the windows was reported. The confinement effect of this cage, containing fixed and isolated gold complexes, was investigated. The results showed that the catalysts in the cage displayed higher reactivity and selectivity compared to the monomeric analogue, and the cage structure prevented the formation of less active dinuclear gold complexes, making it more stable.
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.