Article
Chemistry, Physical
Ewelina Szafoni, Krzysztof Kucinski, Grzegorz Hreczycho
Summary: This article discloses a mild, scalable, and chemoselective cobalt-catalyzed reaction system for the construction of Si-O-Si moieties. The reaction has a broad scope and can be used to synthesize various silicon building blocks, including challenging dihydrosiloxanes and functionalized silsesquioxanes. Importantly, the results are benchmarked with state-of-the-art methods.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Organic
Huaquan Fang, Guoqiang Wang, Martin Oestreich
Summary: The strong boron Lewis acid B(C6F5)(3) has been found to catalyze the reductive rearrangement of oximes and their ether derivatives at room temperature with hydrosilanes as the reducing agents, yielding secondary amine products in good yields. Control experiments and DFT computational analysis revealed three energetically accessible reaction pathways, with the reduction-rearrangement sequence being slightly preferred.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Zhen-Zhen Zhao, Xiaobo Pang, Xiao-Xue Wei, Xue-Yuan Liu, Xing-Zhong Shu
Summary: We report a new method for synthesizing organohydrosilanes from phenols and ketones. This method involves unconventional Si-Cl cleavage and offers a complementary scope to established methods. It can successfully couple aryl- and alkenylhydrosilanes with various electrophiles, and is tolerant of different functional groups. The method has demonstrated gram-scale reactions, incorporation of organohydrosilanes into biologically active molecules, and derivatization of the formed products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Peng Guo, Ling-Chao Cheng, Xinglei He, Ke-Yin Ye
Summary: In this study, we report the development of a highly selective and scalable dehydrogenative hydroxylation of hydrosilanes, using a low loading of Earth-abundant cobalt catalyst, water as a green oxidant, and good generality for various silicon compounds.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Hyune-Jea Lee, Changmo Kwak, Dong-Pyo Kim, Heejin Kim
Summary: In this study, an atom-economic flow approach was developed for the selective and sequential mono-, di-, and tri-functionalizations of unactivated hydrosilanes using serial organolithium reactions catalyzed by earth-abundant metal compounds. The use of t-BuOK as a catalyst enabled rapid reactions of organolithiums with hydrosilanes, leading to efficient generation of functionalized organolithiums and their consecutive reactions with hydrosilanes under mild conditions. The integrated one-flow system allowed for precise reaction control and combinatorial functionalizations of trihydrosilane, providing various tetrasubstituted organosilane libraries.
Article
Crystallography
Sonia Bruna, Isabel Cuadrado, Josefina Perles
Summary: This paper reports on a rare silicon-centered spirocyclic compound and describes its formation mechanism and characterization methods during thermal induction.
Article
Chemistry, Multidisciplinary
Miaomiao Zhou, Ting Wang, Gui-Juan Cheng
Summary: Selective defunctionalization of synthetic intermediates is a valuable approach in organic synthesis, and the recently developed B(C6F5)(3)/hydrosilane-mediated reductive deamination reaction of primary amines has important applications.
FRONTIERS IN CHEMISTRY
(2022)
Article
Chemistry, Organic
En-He Huang, Ying-Qi Zhang, Da-Qiu Cui, Xin-Qi Zhu, Xiao Li, Long-Wu Ye
Summary: A new copper-catalyzed Si-H bond insertion reaction involving N-propargyl ynamides and hydrosilanes has been discovered, providing an efficient method for the practical and atom-economic synthesis of valuable organosilanes in generally moderate to excellent yields under mild reaction conditions. This reaction also introduces a new pathway for Si-H bond insertion involving vinyl cations as key intermediates.
Article
Chemistry, Organic
Xiao-Hua Zhou, Jun-Hui Zhu, Guang-Ao Song, Xin-Li Jiang, Xiao-Jun Fang, Zheng Xu, Li-Wen Xu
Summary: A palladium-catalyzed cross-coupling silylation reaction has been developed for the synthesis of structurally diverse silanes. This method exhibits simplicity, wide substrate scope, high chemoselectivity, and good tolerance towards functional groups. The study highlights the importance of this reaction in the field of organosilicon chemistry.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Yonatan Sukhran, Israel Alshanski, Ofer Filiba, Megan J. Mackintosh, Igor Schapiro, Mattan Hurevich
Summary: Designing and synthesizing orthogonally protected monosaccharide building blocks is important for the controlled preparation of defined oligosaccharides. This study investigates the selective introduction of protecting groups and the unexpected reactivity of a conformationally restricted galactoside. The insights gained from this research offer a new strategy for acylation reactions and can be applied in the synthesis of key monomeric building blocks.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Sven C. Richter, Martin Oestreich
Summary: The chemoselective deoxygenation of secondary benzylic alcohols can be achieved through a series of formylation and reduction reactions, forming formates. In this process, the formyl group acts as both an activator and a self-sacrificing protecting group, allowing the reaction to proceed in the presence of other reducible groups.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Yougourthen Boumekla, Fengjie Xia, Lucas Vidal, Cedric Totee, Christophe Raynaud, Armelle Ouali
Summary: A method to reduce aldimines via hydrosilylation using a catalytic system of calcium triflimide and potassium hexafluorophosphate is reported, achieving high yields in mild conditions. Additionally, a bioactive molecule with antifungal properties was successfully synthesized on a large scale in environmentally friendly solvent. The mechanism involves electrophilic activation of the silane by the calcium catalyst, as confirmed by experimental and DFT calculations.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Joschua Helmer, Alexander Hepp, Felicitas Lips
Summary: The reductive debromination of {N(SiMe3)Ph}SiBr3 yields a zwitterionic six-vertex amido-substituted silicon cluster, which forms adducts with NHCMe4 and DMAP. The NHC adduct further coordinates to BH3. Additionally, the silicon cluster can undergo addition with MeI and iodine to form halogenated silicon clusters.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Yesmin Akter Rina, Joseph A. R. Schmidt
Summary: We report an attractive and efficient synthetic approach to form Si-N bonds via the heterodehydrocoupling of silanes and amines catalyzed by a lanthanum-based N,N-dimethylbenzylamine complex [La(DMBA)(3)]. This method allows for the formation of numerous silylamines in high efficiency and moderate-to-excellent yields under mild conditions.
Article
Chemistry, Organic
Wangbing Li, Zhichao Lu, Gerald B. Hammond, Bo Xu
Summary: The use of an unbalanced ion pair promoter accelerates nucleophilic fluorinations, and conversion of ion exchange resin to a polymer-supported ion pair promoter allows for reuse in continuous flow conditions with good water tolerance.
Article
Chemistry, Applied
Tomas Beranek, Martin Kos, Lubomir Vana, Ivana Cisarova, Jan Sykora, Jan Storch, Vladimir Cirkva, Martin Jakubec
Summary: Six helicene based push-pull systems were designed and synthesized to modify the optical properties of the helicene skeleton. The properties of the compounds were studied by DFT calculations and spectroscopic methods. The introduction of a diphenylaminophenylene group as a donor led to an increase in fluorescence quantum yield and a dependence on solvent polarity.
Article
Biochemistry & Molecular Biology
Janaki Devi Somasundaram, Arash Ebrahimi, Sreejith P. Nandan, Alexey Cherevan, Dominik Eder, Miroslava Supolikova, Eva Novakova, Robert Gyepes, Lukas Krivosudsky
Summary: A series of five decavanadate complexes were successfully synthesized using a one-pot synthesis. The structures and properties of these complexes were studied, and it was found that 1 and 3 are decavanadato complexes, while 2, 4, and 5 are decavanadate complex salts. The binding to model proteins, cytotoxicity, and water oxidation catalysis were investigated, and it was observed that 1 showed higher activity in water oxidation catalysis and lower cytotoxicity compared to the uncoordinated V-10.
JOURNAL OF INORGANIC BIOCHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Tereza Duskova, Dharmendra S. Prajapati, Pavel Kaule, Lucie Cervenkova Stastna, Tomas Strasak, Jan Cermak
Summary: A series of imidazolium salts with specific substituents were synthesized and used as precursors for the synthesis of rhodium and iridium complexes. The complexes exhibited high fluorophilicity, making them suitable for organic-organic and organic-fluorous phase separation.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Nikolas Kiraly, Dominika Capkova, Robert Gyepes, Nikola Vargova, Tomas Kazda, Jozef Bednarcik, Daria Yudina, Tomas Zelenka, Pavel Cudek, Vladimir Zelenak, Anshu Sharma, Vera Meynen, Virginie Hornebecq, Andrea Strakova Fedorkova, Miroslav Almasi
Summary: Two new alkaline earth metal-organic frameworks, UPJS-15 and UPJS-16, were synthesized and characterized. UPJS-15 exhibited one-dimensional channels with a size of approximately 11 x 10 angstrom(2) and showed high adsorption capacity for CO2. UPJS-16, on the other hand, did not show significant adsorption for the tested gases.
Article
Chemistry, Multidisciplinary
Timothee Cadart, Tim Glasel, Ivana Cisarova, Robert Gyepes, David Necas, Marko Hapke, Martin Kotora
Summary: Catalytic cyclotrimerization routes to symmetrical [9]helical indenofluorene were investigated using various transition-metal complexes and thermal conditions. The cyclotrimerizations could be accompanied by dehydro-Diels-Alder reaction, resulting in another type of aromatic compounds. The structures of both the symmetrical [9]helical cyclotrimerization product and the dehydro-Diels-Alder product were confirmed by single-crystal X-ray diffraction analyses. Enantioselective cyclotrimerization limits were also examined, and DFT calculations provided insights into the reaction course and the origin of decreased enantioselectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Biochemistry & Molecular Biology
Michaela Rendosova, Robert Gyepes, Martin Kello, Maria Vilkova, Dagmar Mudronova, Petra Olejnikova, Paola Cardiano, Sofia Gama, Demetrio Milea, Zuzana Vargova
Summary: Two silver(I) complexes with biologically relevant heterocyclic ligands, pyrrole and furan-2-carboxylic acid, were synthesized and characterized. Their solubility and stability were confirmed in biological test solutions using 1H NMR spectroscopy. The complexes showed significant antimicrobial and anticancer activity, with high selectivity against specific microorganisms and cell lines. The importance of these complexes in biomedical research is rated as 8 out of 10.
JOURNAL OF INORGANIC BIOCHEMISTRY
(2023)
Article
Biochemical Research Methods
Lenka Michalkova, Stepan Hornik, Jan Sykora, Vladimir Setnicka, Bohus Bunganic
Summary: Nuclear magnetic resonance (NMR) metabolomics was used to identify metabolic changes in pancreatic cancer (PC) blood plasma samples. Discrimination between PC stages and control groups was achieved with high accuracy. A predictive model based on discriminant analyses identified individuals at risk of pancreatic pathology development.
JOURNAL OF PROTEOME RESEARCH
(2023)
Article
Biochemistry & Molecular Biology
Lucia Pincekova, Eva Janciova, Dusan Berkes, Robert Gyepes, Andrej Kolarovic, Ol'ga Caletkova
Summary: The total synthesis of the 2-formylpyrrole alkaloid hemerocallisamine I is achieved in both racemic and enantiopure forms. The synthesis involves the use of (2S,4S)-4-hydroxyglutamic acid lactone as a key intermediate, with crystallization-induced diastereomer transformation used to introduce the target stereogenic centers. A crucial step in the synthesis is the Maillard-type condensation for constructing the desired pyrrolic scaffold.
Article
Chemistry, Inorganic & Nuclear
Bela Urban, David Dunlop, Robert Gyepes, Pavel Kubat, Kamil Lang, Michal Horacek, Jiri Pinkas, Ludmila Simkova, Martin Lamac
Summary: Neutral zirconocene complexes were synthesized and converted to their cationic counterparts by chloride abstraction. The cationic complexes exhibited enhanced luminescence properties. The structures of the complexes were characterized by X-ray diffraction, their electrochemistry was investigated by cyclic voltammetry, and their photophysical properties were studied with quantum-chemical calculations.
Article
Engineering, Chemical
Alena Krupkova, Monika Muellerova, Roman Petrickovic, Tomas Strasak
Summary: The performance of commercial cellulose membranes with pore size on the border between ultra-and nano-filtration in selected organic solvents was studied. The rejection of small solutes and applicability for dendrimer purification were the main focuses of this study. The results showed that solute molar volume and polarity type, expressed by Hansen solubility parameters, were crucial factors affecting rejection, and the spatial arrangement became important with increasing size of solute molecule. The solvent composition also influenced the membrane structure, resulting in a decrease of membrane molecular weight cutoff.
SEPARATION AND PURIFICATION TECHNOLOGY
(2023)
Article
Biochemistry & Molecular Biology
Monika Mullerova, Michaela Hovorkova, Tana Zavodna, Lucie Cervenkova Stastna, Alena Krupkova, Vojtech Hamala, Katerina Novakova, Jan Topinka, Pavla Bojarova, Tomas Strasak
Summary: Galectins and their carbohydrate ligands play a vital role in regulating various biological processes. Carbosilane dendrimers show promise as a nanoscaffold for presenting multivalent carbohydrate ligands to target galectin receptors. This study presents a synthetic method for lactose-functionalized carbosilane glycodendrimers and demonstrates their high affinity to galectin-9. Multivalent presentation of the ligand significantly enhances its inhibitory effect, as shown by the 1400-fold higher potency of the third-generation dendritic ligand compared to monovalent lactose. The increased affinity is attributed to the formation of stable galectin/lactose-functionalized carbosilane glycodendrimer aggregates.
Article
Chemistry, Physical
Martin Lamac, Bela Urban, Michal Horacek, Daniel Buzek, Lucie Leonova, Ales Styskalik, Anna Vykydalova, Karel Skoch, Matous Kloda, Andrii Mahun, Libor Kobera, Kamil Lang, Michael G. S. Londesborough, Jan Demel
Summary: The study reveals that activated borane (ActB) can act as a heterogeneous catalyst in hydrosilylation/deoxygenation reactions and gas-phase dehydration of ethanol, showing potential for tuning catalytic reaction outcomes and high activity.
Article
Biochemistry & Molecular Biology
Michaela Rendosova, Robert Gyepes, Simona Sovova, Danica Sabolova, Maria Vilkova, Petra Olejnikova, Martin Kello, Boris Lakatos, Zuzana Vargova
Summary: A series of novel Ga(III)-pyridine carboxylates were successfully synthesized by a simple one-step procedure. The molecular structure, inter and intramolecular interactions, and their influence on spectral and thermal properties were confirmed by various analysis techniques. The complex species speciation, antimicrobial activity, and anticancer activity were investigated, as well as the binding activity between the complexes and bovine serum albumin.
JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY
(2023)