Article
Chemistry, Multidisciplinary
Tobias Brueckner, Felipe Fantuzzi, Tom E. Stennett, Ivo Krummenacher, Rian D. Dewhurst, Bernd Engels, Holger Braunschweig
Summary: The study found that NHC-stabilised diboryne can undergo a high-yielding reaction with tetraethyldiphosphine at room temperature to form a B2P2 heterocycle, which can be oxidised to different ionic forms. With each oxidation step, the structure of the heterocycle changes, showing different forms.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jinxiong Lin, Friedrich Wossidlo, T. Coles Nathan, Manuela Weber, Simon Steinhauer, Tobias Boettcher, Christian Mueller
Summary: In this study, a phosphinine-borane adduct was synthesized and characterized for the first time using crystallography. The reaction heavily depends on the substituents in the phosphorus heterocycle. In contrast, the reaction of B2H6 with different substituted phosphinines leads to an equilibrium between the starting materials and the adducts, determined by the Lewis basicity. The novel phosphinine-borane adduct exhibits rapid and facile reactivity towards phenylacetylene, forming a previously unknown dihydro-1-phosphabarrelene with styrene.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Jinxiong Lin, Friedrich Wossidlo, T. Coles Nathan, Manuela Weber, Simon Steinhauer, Tobias Boettcher, Christian Mueller
Summary: In this study, a phosphinine-borane adduct was synthesized and characterized for the first time. Additionally, a novel phosphabarrelenium salt was discovered.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Fabian Roesler, Mate Kovacs, Clemens Bruhn, Zsolt Kelemen, Rudolf Pietschnig
Summary: A transition metal-free route to phosphetes with an exocyclic alkene unit is proposed, where phosphanides are added to diynes to form phosphaallylic intermediates that can transform into phosphetes or phospholes depending on reaction conditions. The study suggests that phosphole formation is thermodynamically controlled, while kinetic control leads to the formation of phosphetes. Structural and luminescence properties of the rare class of phosphetes and key intermediates are investigated.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Peter Coburger, Clara Schweinzer, Zhongshu Li, Hansjoerg Gruetzmacher
Summary: The reaction of IDP with trityl phosphaalkyne leads to the formation of a mixture containing molecules 1a and 1b with a C3P3 core carrying a two-fold negative charge. In order to avoid the formation of an antiaromatic 8 pi electron system, 1a adopts a bicyclic [3.1.0] structure and 1b a tricyclic [2.2.0.0] structure, which are in dynamic equilibrium. 1a and 1b can be reversibly oxidized to [5](2+), a triphosphinine dication with a flat aromatic C3P3 ring, through a two-electron redox reaction mediated by the 7 pi-radical cation [4](center dot+).
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Johannes Nebauer, Christian Neiss, Marcel Krug, Alexander Vogel, Dominik Fehn, Shuhei Ozaki, Frank Rominger, Karsten Meyer, Kenji Kamada, Dirk M. Guldi, Andreas Goerling, Milan Kivala
Summary: This article describes a new type of nitrogen-centered polycyclic scaffold synthesized through intramolecular oxidative cyclodehydrogenation of tri(1-naphthyl)amine, which is the first example of a direct 3-fold cyclization of a triarylamine under oxidative conditions. Experimental and theoretical studies reveal the impact of cyclization on the electronic and photophysical properties, and mechanistic studies suggest the cyclization occurs under kinetic control via a dicationic mechanism.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Jingyang Qin, Manuel Barday, Samikshan Jana, Nil Sanosa, Ignacio Funes-Ardoiz, Christopher J. Teskey
Summary: A mild and selective hydropyridylation method for dienes was reported, allowing for traceless coupling of dienes on a wide range of pyridine substrates. The method showed good functional group tolerance, making it suitable for late-stage functionalization. The mechanistic pathway involved non-reversible hydrogen atom transfer, resulting in a reaction that was uniquely selective for dienes in the presence of other olefins.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Markus R. P. Pielmeier, Tom Nilges
Summary: Phosphorene and SnIP are two-dimensional and one-dimensional semiconductors formed from black phosphorus and SnI2, synthesized through mineralization and short way transport with similar yet different preparation methods. Investigating the formation mechanisms of these two compounds is of crucial importance for energy conversion, storage, and catalysis applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Chenxiao Qi, Guillaume Force, Vincent Gandon, David Leboeuf
Summary: A novel method for haloamidation is introduced in this paper, providing new building blocks for drug discovery. This method overcomes some limitations of traditional reactions and the reaction mechanism is deeply studied, which is expected to promote the development of more complex transformations in this field.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Yong Wu, Shanshan Cao, Iskander Douair, Laurent Maron, Xihe Bi
Summary: The [2+1] cycloaddition reaction of a metal carbene with an alkene often suffers from side reactions, leading to lower yields of cyclopropanation products. By adding a low concentration of diazo compound to alkenes, it was found that AgOTf catalysis can efficiently produce cyclopropane products from hindered alkenes.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Adam N. Barrett, Martin Diefenbach, Mary F. Mahon, Vera Krewald, Ruth L. Webster
Summary: In this study, gram-scale quantities of 2,4,6-tris(triphenylmethyl)-Dewar-1,3,5-triphosphabenzene were synthesized using an alkyne cyclotrimerization regime. It was found that this compound can undergo rearrangement and phosphorus migration reactions to form ring-contracted species. Additionally, novel crystallographically characterized products of other transformations were reported.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Marin Puget, Viacheslav Shcherbakov, Sergey Denisov, Philippe Moreau, Jean-Pierre Dognon, Mehran Mostafavi, Sophie Le Caer
Summary: The nature of the primary species formed in FEC depends on the amount of FEC in the solution, which will affect its performance in the electrolyte.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Zhiyao Duan, Graeme Henkelman
Summary: This study uses global optimization and constant-potential density functional theory to simulate the complete process of Pt dissolution, revealing the formation and dissolution mechanism of a two-dimensional Pt surface oxide. The findings provide a fundamental understanding of Pt dissolution under potential cycling, which is essential for the rational design of durable Pt-based cathodes for fuel cells.
Article
Chemistry, Multidisciplinary
Yun Xiong, Shicheng Dong, Shenglai Yao, Jun Zhu, Matthias Driess
Summary: New types of metal-free white phosphorus activation have been reported, leading to the synthesis of compounds 2 and 4 with unique structures. The effectiveness of this method has been confirmed through experiments, and its mechanism has been investigated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Elzbieta Regulska, Philip Hindenberg, Adrian Espineira-Gutierrez, Carlos Romero-Nieto
Summary: Linearly-fused diphosphaarenes are a novel family of molecules with striking optoelectronic properties and outstanding stability, which hold great importance in materials science.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Peter Coburger, Clara Schweinzer, Zhongshu Li, Hansjoerg Gruetzmacher
Summary: The reaction of IDP with trityl phosphaalkyne leads to the formation of a mixture containing molecules 1a and 1b with a C3P3 core carrying a two-fold negative charge. In order to avoid the formation of an antiaromatic 8 pi electron system, 1a adopts a bicyclic [3.1.0] structure and 1b a tricyclic [2.2.0.0] structure, which are in dynamic equilibrium. 1a and 1b can be reversibly oxidized to [5](2+), a triphosphinine dication with a flat aromatic C3P3 ring, through a two-electron redox reaction mediated by the 7 pi-radical cation [4](center dot+).
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Oncology
Annette G. Beck-Sickinger, Daniel P. Becker, Oksana Chepurna, Bhaskar Das, Sebastian Flieger, Evamarie Hey-Hawkins, Narayan Hosmane, Satish S. Jalisatgi, Hiroyuki Nakamura, Rameshwar Patil, Maria da Graca H. Vicente, Clara Vinas
Summary: This article summarizes current research on the development of boron delivery drugs for boron neutron capture therapy, which were presented and discussed at the National Cancer Institute (NCI) Workshop on Neutron Capture Therapy held on April 20-22, 2022. The most commonly used boron sources are icosahedral boron clusters attached to various molecules such as peptides, proteins, porphyrin derivatives, dendrimers, polymers, and nanoparticles, as well as encapsulated into liposomes. These boron clusters and/or carriers can be labeled with contrast agents, allowing for imaging techniques like PET, SPECT, and fluorescence to quantify tumor-localized boron and serve as theranostic agents.
CANCER BIOTHERAPY AND RADIOPHARMACEUTICALS
(2023)
Article
Chemistry, Multidisciplinary
Nils Koenig, Yokari Godinez-Loyola, Yang Fangshun, Christian Laube, Michael Laue, Peter Loennecke, Cristian A. Strassert, Evamarie Hey-Hawkins
Summary: Phosphole oxides react with sulfonyl isocyanates, forming sulfonylimino phospholes in high yields. This facile modification allows for the synthesis of new phosphole-based aggregation-induced emission (AIE) luminogens with high fluorescence quantum yields in the solid state. Changing the chemical environment of the phosphorus atom of the phosphole framework results in a significant red-shift of the fluorescence maximum.
Article
Pharmacology & Pharmacy
Sebastian Braun, Svetlana Paskas, Markus Laube, Sven George, Bettina Hofmann, Peter Loennecke, Dieter Steinhilber, Jens Pietzsch, Sanja S. Mijatovic, Danijela Maksimovic-Ivanic, Evamarie Hey-Hawkins
Summary: In this study, carborane-containing dual COX-2/5-LO inhibitors were designed by incorporating metabolically stable, sterically demanding, and hydrophobic carboranes into existing inhibitors. Five carborane-containing derivatives showed high inhibitory activities towards COX-2 and 5-LO, with meta-carborane derivative 3 demonstrating higher anticancer activity compared to RWJ-63556. The accumulation of lipid droplets in cells indicated the blockage of COX-2 and 5-LO pathways, suggesting a promising approach for the design of potent dual COX-2/5-LO inhibitors.
ADVANCED THERAPEUTICS
(2023)
Article
Chemistry, Multidisciplinary
Kyzgaldak Ramazanova, Peter Loennecke, Evamarie Hey-Hawkins
Summary: The reactive P-N bond in a racemic mixture of endo-1-phospha-2-azanorbornene (PAN) is cleaved with enantiomerically pure lithium alkoxides and protonation to produce diastereomeric mixtures of P-chiral 1-alkoxy-2,3-dihydrophosphole derivatives. The isolation of these compounds is challenging due to the reversibility of the reaction, but methylation and sulfur protection prevent elimination reaction. The resulting P-chiral diastereomeric 1-alkoxy-2,3-dihydrophosphole sulfide mixtures can be easily separated and characterized, and can be reduced to phosphorus(III) P-stereogenic 1-alkoxy-2,3-dihydrophospholes for use in asymmetric homogeneous transition metal catalysis.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Biochemistry & Molecular Biology
Joerg Matysik, Luca Gerhards, Tobias Theiss, Lisa Timmermann, Patrick Kurle-Tucholski, Guzel Musabirova, Ruonan Qin, Frank Ortmann, Ilia A. Solov'yov, Tanja Gulder
Summary: This review summarizes the phenomenon of nuclear hyperpolarization occurring in chemical reactions, known as CIDNP or photo-CIDNP if driven by light. It occurs in both liquid and solid-state, often involving electron transfer systems with flavins as electron acceptors. The article explains the properties of flavins, their occurrence in spin-correlated radical pairs (SCRPs), and the potential involvement of flavin-carrying SCRPs in animal magneto-reception at Earth's magnetic field.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Review
Biochemistry & Molecular Biology
Zeno Fickenscher, Evamarie Hey-Hawkins
Summary: Inspired by the role of multimetallic assemblies in enzyme catalysis, a wide range of heterobimetallic complexes have been developed for use in homogeneous catalysis. These complexes, starting from simple ones with s-donating and p-accepting ligands, have evolved into more complex systems over the past two decades. The presence of a second metal center in the active catalyst allows for new reaction pathways and significantly increased catalytic activity. This review focuses on the mechanistic aspects of heterobimetallic complexes in homogeneous catalysis, showcasing their versatility and the different types of interactions and reactions they enable.
Article
Biochemistry & Molecular Biology
Zeno B. G. Fickenscher, Peter Loennecke, Anna K. Mueller, Oldamur Holloczki, Barbara Kirchner, Evamarie Hey-Hawkins
Summary: Two heterometallic Mo,M' complexes (M' = Ir-III, Rh-III) were synthesized and characterized. They showed a significant synergistic effect, especially Mo and Ir, leading to a fourfold increase in catalytic activity compared to a binary mixture of the monometallic counterparts. The mechanism of CO2 hydrogenation to formate by a monometallic Ir-III catalyst was studied, revealing the importance of the metal-base adduct and inner-sphere hydride transfer.
Article
Biochemistry & Molecular Biology
Sebastian Braun, Sanja Jelaca, Markus Laube, Sven George, Bettina Hofmann, Peter Loennecke, Dieter Steinhilber, Jens Pietzsch, Sanja Mijatovic, Danijela Maksimovic-Ivanic, Evamarie Hey-Hawkins
Summary: Targeting inflammatory mediators and related pathways is a rational strategy for cancer treatment. Incorporating carboranes into dual COX-2/5-LO inhibitors shows promise, with compounds exhibiting high 5-LO inhibitory activities. However, carborane analogs demonstrate lower anticancer activity compared to related compounds in cell viability studies. R-830-Cb, a carborane-based analog, shows potential for further mechanistic and in vivo studies due to the advantages of boron cluster incorporation.
Article
Pharmacology & Pharmacy
Liridona Useini, Teodora Komazec, Markus Laube, Peter Loennecke, Jonas Schaedlich, Sanja Mijatovic, Danijela Maksimovic-Ivanic, Jens Pietzsch, Evamarie Hey-Hawkins
Summary: Nonsteroidal anti-inflammatory drugs (NSAIDs) are widely used for pain, fever, and inflammation, and have reported antitumor properties. Selectivity for the COX-2 isoform of NSAIDs is of high interest to reduce off-target effects. Modified NSAIDs using carborane clusters show altered selectivity profile and isonimesulide and its carborane derivatives exhibit stronger antitumor potential compared to nimesulide and isonimesulide. Additionally, replacement of the phenyl ring with a carborane moiety shifts the COX activity from nonactive to active compounds.
ADVANCED THERAPEUTICS
(2023)
Article
Pharmacology & Pharmacy
Ivana Predarska, Mohamad Saoud, Valentin Cepus, Evamarie Hey-Hawkins, Goran N. Kaluderovic
Summary: This article investigates the effects of oxaliplatin and its derivatives on different tumor types, and designs platinum(IV) platforms based on oxaliplatin to assess their antitumor capacity against various breast cancer cell lines.
ADVANCED THERAPEUTICS
(2023)
Article
Chemistry, Physical
Nils Koenig, Yokari Godinez-Loyola, Hendrik Weiske, Sergej Naumov, Peter Loennecke, Ralf Tonner-Zech, Cristian A. Strassert, Evamarie Hey-Hawkins
Summary: In this study, a facile synthetic strategy for obtaining propeller-rich molecules bearing a thieno[3,2-b]phosphole motif was reported via MnIII-mediated oxidative annulation reaction. All synthesized compounds showed aggregation-induced emission (AIE) characteristics, strong fluorescence in the solid state, and the photophysical properties were dependent on the substituents. The phosphinated thieno[3,2-b]phospholes exhibited a high degree of restrictions on intramolecular motions, leading to powerful solid-state light emitters with fluorescence quantum yields close to 100% and lifetimes up to 7.9 ns, even at room temperature.
CHEMISTRY OF MATERIALS
(2023)
Editorial Material
Chemistry, Multidisciplinary
Kyzgaldak Ramazanova, Peter Loennecke, Evamarie Hey-Hawkins
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Lisa Koehler, Wolfgang Gaertner, Georgeta Salvan, Jorg Matysik, Christian Wiebeler, Chen Song
Summary: Recently, novel phytochromes called cyanobacteriochromes (CBCRs) have been discovered. CBCRs are attractive for further research and design of fine-tuned photoswitches for optogenetics due to their related photochemistry and simpler structure. However, there is limited mechanistic data on the factors controlling absorbance changes in CBCRs. This study presents a simple method to isolate four photocycle intermediates of Slr1393g3 for NMR use.
Article
Chemistry, Inorganic & Nuclear
Saral Baweja, Tom Gabler, Peter Loennecke, Evamarie Hey-Hawkins
Summary: Transition metal coordination chemistry and catalysis often employ phosphine ligands, among which phosphine aldehydes are relatively understudied. In this study, we synthesized 3-(diphenylphosphino)propanal (PCHO) and investigated its complexation behavior with Pd(II) and Pt(II). The catalytic activity of the Pd(II) phosphine aldehyde complexes was examined in Cu-free Sonogashira and Suzuki-Miyaura cross-coupling reactions, confirming the homogeneous nature of the catalytically active species.
DALTON TRANSACTIONS
(2023)
