Review
Chemistry, Organic
Cui Yin, Zhang Guofu, Ding Chengrong
Summary: This article systematically summarizes the development and mechanism of Lossen rearrangement, as well as discusses its future research direction and application prospects.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Kotaro Ishihara, Takayuki Shioiri, Masato Matsugi
Summary: A novel method using diphenyl phosphorazidate was developed for the synthesis of carbamoyl azides from hydroxamic acids. This method avoids the use of highly explosive reagents and allows the conversion of various hydroxamic acids into the corresponding carbamoyl azides.
TETRAHEDRON LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Changwei Chen, Hongyu Zhang, Gang Xu, Sunliang Cui
Summary: This study demonstrates the oxoarylation of ynamides with N-aryl hydroxamic acids, and probes the mechanism and scalability through deuterium-labelling reaction and gram-scale reaction.
CHINESE CHEMICAL LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Cheng Xu, Zhen Ye, Li Xiang, Shuhan Yang, Qian Peng, Xuebing Leng, Yaofeng Chen
Summary: The synthesis of silacycle compounds, including the insertion of metal-substituted silylene fragments into the aromatic ring of naphthalene, is of both fundamental and application importance. This insertion is followed by interesting rearrangements to yield silaspiro-benzocycloheptenyl and cyclobutenosilaindan derivatives, with mechanistic aspects revealed through DFT investigations. Additionally, formed cyclobutenosilaindan potassium can readily react with various compounds to afford substituted cyclobutenosilaindans in high yields.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemistry & Molecular Biology
Min Gao, Yong-Qi Ding, Jia-Bi Ma
Summary: This study reports on the N-2 adsorption on well-defined Y2C4H0,1- cluster anions under mild conditions. The results show that N-2 adsorption on Y2C4H- clusters is 50 times more reactive than on Y2C4- clusters. Further analysis reveals the important role of the H atom in modifying the charge distribution and facilitating the approach of N-2 to Y2C4H-.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Article
Chemistry, Multidisciplinary
Hsiang-Yu Chuang, Manuel Schupp, Ricardo Meyrelles, Boris Maryasin, Nuno Maulide
Summary: A selenium-catalysed para-hydroxylation of N-aryl-hydroxamic acids is reported in this study. The mechanism involves N-O bond cleavage and selenium-induced [2,3]-rearrangement to deliver para-hydroxyaniline derivatives. This redox-neutral transformation provides a new synthetic approach to para-aminophenols.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Maike Lettow, Kim Greis, Eike Mucha, Tyler R. Lambeth, Murat Yaman, Vasilis Kontodimas, Christian Manz, Waldemar Hoffmann, Gerard Meijer, Ryan R. Julian, Gert von Helden, Mateusz Marianski, Kevin Pagel
Summary: Fucose is a signaling carbohydrate attached to the end of glycan processing. It has various roles in processes like leukocyte adhesion and pathogen-receptor interactions. However, the presence of fucose-containing chimeric fragments in mass-spectrometric analysis has complicated the determination of glycans' structure. In this study, various techniques were used to deduce the rearrangement product of fucose in model trisaccharides Lewis x and blood group H2, with the most likely product being fucose attached to galactose through an alpha(1 -> 6) glycosidic bond.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Medicinal
Elena Lenci, Andrea Angeli, Lorenzo Calugi, Riccardo Innocenti, Fabrizio Carta, Claudiu T. Supuran, Andrea Trabocchi
Summary: A series of D-proline peptidomimetics were found to act as dual inhibitors of human carbonic anhydrases and human gelatinases, potentially offering a new treatment approach for gastric cancer.
EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY
(2021)
Article
Pharmacology & Pharmacy
Rowoon Lee, Vitchan Kim, Youngjin Chun, Donghak Kim
Summary: The human genome contains four cytochrome P450 2C subfamily enzymes, with CYP2C8 attracting research interest due to drug-drug interactions and various polymorphic outcomes. Directed evolution analysis was used to study the catalytic activity of CYP2C8, resulting in mutants with increased activity, particularly the V237A mutant showing stronger substrate binding affinity.
Article
Chemistry, Multidisciplinary
Mathias Paul, Katrin Peckelsen, Thomas Thomulka, Jonathan Martens, Giel Berden, Jos Oomens, Joerg-M. Neudoerfl, Martin Breugst, Anthony J. H. M. Meijer, Mathias Schaefer, Albrecht Berkessel
Summary: The study reported in this paper focuses on the preparation of charge-tagged Breslow intermediates/keto tautomers derived from three different types of NHCs and aldehydes. Using ESI-MS IR ion spectroscopy, it was confirmed that in the gas phase, the Breslow intermediates derived from imidazolidin-2-ylidenes exist as diamino enols, while those derived from 1,2,4-triazolin-5-ylidenes and thiazolin-2-ylidenes exist as keto tautomers. This observation is consistent with findings in solution and in the crystalline state.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Jaya Mehara, Adarsh Koovakattil Surendran, Teun van Wieringen, Deeksha Setia, Cina Foroutan-Nejad, Michal Straka, Lubomir Rulisek, Jana Roithova
Summary: Gold(II) complexes are not commonly used in catalyzing chemical transformations due to their easy oxidation or reduction to more stable gold(III) or gold(I) complexes. In this study, we investigated the thermodynamics, stability, and spectral properties of [Au-II(L)(X)](+) complexes (L=ligand, X=halogen) in the gas phase. It was found that bidentate and tridentate ligands with nitrogen donor atoms are the best choices for stabilizing gaseous [Au-II(L)(X)](+) complexes. Quantum chemical calculations revealed that the molecular and electronic structures, as well as the spectroscopic properties, of the investigated gold(II) complexes are similar to those of stable copper(II) complexes.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Siou-Wei Liang, Yingjie Guo, Wan-Ching Lee, Pin-Rui Zeng, Tzu-Hao Lin, Pei-Zhen Xie, Hsuan-Hao Kang, I-Chung Lu, Yu-Chang Chang
Summary: Two newly designed Pd(II) precatalysts were synthesized and used to efficiently convert unreactive aryl chlorides, benzyl chlorides, and benzoyl chlorides. The deprotonation of the precatalysts led to the dissociation of NHC, and the proposed Pd(II) species could be reduced to Pd(0) using ethoxide. The size of salt additive cations and the basicity of the base were found to influence the catalytic properties.
Article
Chemistry, Analytical
Lu Yang, Brad Methven, Zoltan Mester, Juris Meija
Summary: Isotopic analysis by mass spectrometry relies on certified reference materials (CRMs) to correct instrumental isotopic fractionation. The currently recognized reference material for copper isotope ratio, SRM976, is no longer available. In this study, an independent isotope ratio measurement of a high-purity copper CRM, HICU-1, was reported and its isotopic composition was shown to be nearly identical to that of NIST SRM976.
JOURNAL OF ANALYTICAL ATOMIC SPECTROMETRY
(2023)
Article
Geochemistry & Geophysics
Xiancheng Shao, Guoyuan Wu, Gongliang Jiang, Ye Wang, Shikun Pu, Yaozhong Lan, Dengbang Jiang
Summary: The recovery of rare earth elements from ores is of great importance in modern technology. Bastnaesite can be purified by flotation and doping with La can enhance its recovery. The presence of Al minerals should be minimized as they reduce the flotation efficiency of bastnaesite.
Article
Chemistry, Multidisciplinary
Maximilian Rang, Felipe Fantuzzi, Merle Arrowsmith, Ivo Krummenacher, Eva Beck, Robert Witte, Alexander Matler, Anna Rempel, Tobias Bischof, Krzysztof Radacki, Bernd Engels, Holger Braunschweig
Summary: The one-electron reduction of a cyclic (alkyl)(amino)carbene (CAAC)-stabilized arylborylene carbonyl complex yields a dimeric borylketyl radical anion, leading to a highly nucleophilic dianionic (boraneylidene)methanolate. Computational analyses support the existence of a radical anion intermediate in this process.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Spectroscopy
Jana Roithova, Joost M. Bakker
Summary: This review focuses on ion spectroscopy studies of complexes relevant for methane activation with metal ions and clusters, exploring the interaction between intact methane molecules and metal ions, as well as the spectroscopic characterization of activation products of metal-methane reactions. Recent research has shifted towards investigating interactions between methane and metal clusters.
MASS SPECTROMETRY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Jaya Mehara, Brandon T. Watson, Anurag Noonikara-Poyil, Adway O. Zacharias, Jana Roithova, H. V. Rasika Dias
Summary: This paper investigates the interactions between copper(I), silver(I), and gold(I) metals and pi-ligands, showing that these interactions are influenced by the electron-donating and electron-withdrawing substituents of the ancillary ligands.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Roelant Hilgers, Sin Yong Teng, Anamarija Bris, Aleksandr Y. Pereverzev, Paul White, Jeroen J. Jansen, Jana Roithova
Summary: This study introduces a simple and rapid method for determining enantioselectivities based on mass spectrometry. By using ion mobility separation and delayed reactant labeling experiments, the method can link mass spectra with reaction kinetics to predict the enantioselectivity of the overall reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Jan Zelenka, Aleksandr Pereverzev, Ullrich Jahn, Jana Roithova
Summary: This study investigates the reactivity of reactive radicals generated from sulfonyl azides through photocatalytic activation, and their involvement in C-H activation reactions. The reactivities of these radicals are found to be influenced by different mechanisms, which provide theoretical basis for controlling the reactivity of these intermediates.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Xiaofei Chen, Quentin Duez, Guilherme L. Tripodi, Pieter J. Gilissen, Dimitrios Piperoudis, Paul Tinnemans, Johannes A. A. W. Elemans, Jana Roithova, Roeland J. M. Nolte
Summary: In this study, the mechanistic process of alkene epoxidation mediated by achiral and chiral manganese(V)oxo porphyrin cage complexes was investigated using ion mobility mass spectrometry. The results show that the oxo ligand on the outside of the cage reacts faster with the substrate than the oxo ligand on the inside, indicating how the catalytic activity of the macrocyclic porphyrin complex can be tuned.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biochemical Research Methods
Aleksandr Pereverzev, Jana Roithova
Summary: This perspective provides an overview of action spectroscopy methods for measuring electronic, vibrational, and rotational spectra of mass-selected ions in the gas phase. The existing experimental approaches are classified and summarized. The authors address the issue of multiple names for the same techniques and suggest using commonly used terms to simplify and unify the notation in ion spectroscopy. They believe that this can make the field more accessible to experts outside the mass spectrometry community and have a significant impact on the applications of gas-phase action ion spectroscopy.
JOURNAL OF MASS SPECTROMETRY
(2022)
Editorial Material
Biochemical Research Methods
Aleksandr Y. Pereverzev, Jana Roithova
JOURNAL OF MASS SPECTROMETRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Rob Bakker, Abhinav Bairagi, Monica Rodriguez, Guilherme L. Tripodi, Aleksandr Y. Pereverzev, Jana Roithova
Summary: Cobalt(III)peroxo complexes were studied to investigate the effect of hydrogen bonding on the O2 binding energy and the O-O bond activation. The results showed that hydrogen bonding stabilized the cobalt(III)peroxo core by 10-20 kJ mol-1. The introduction of the first amino group had the largest stabilization effect, while additional amino groups did not significantly change the results. The amino group could transfer a hydrogen atom to the peroxo ligands, leading to O-O bond cleavage with thermodynamic favorability but entropic disfavorability.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Monica Rodriguez, Aleksandr Y. Pereverzev, Jana Roithova
Summary: A novel octahedral non-heme iron-acyl-nitrenoid complex was presented, and its reactivity was studied using a flow chemistry setup with online mass spectrometry detection. It was found that the iron-acyl-nitrenoid complex can activate C-H bonds via hydrogen-atom transfer and form new N-S bonds in the reaction with thiophenol. However, the reaction with hydrocarbons results in the activation of C-H bonds without a subsequent rebound process.
Article
Chemistry, Multidisciplinary
Erik Andris, Michal Straka, Jan Vrana, Ales Ruliska, Jana Roithova, Lubomir Rulisek
Summary: Gold(I) centers can form moderately strong (Au...H) hydrogen bonds with tertiary ammonium groups, but similar hydrogen bonding interactions with isoelectronic silver(I) or copper(I) centers are unknown. The replacement of Cl with Br or I in 3AuCl(+) had only a small effect on the Au...H bond strength. Experimental and computational results showed that the Ag...H and Cu...H interactions were only marginal in the complexes studied, while a Cl...H hydrogen bond was formed. However, when less flexible ligands were used, the presence of Ag...H and Cu...H hydrogen bonds with similar strength to the Au...H bond in 3AuCl(+) was predicted.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Jaya Mehara, Jana Roithova
Summary: Copper(II) complexes with N-oxyl reagents like TEMPO can selectively oxidize alcohols to aldehydes or ketones. Intermediate copper complexes were theoretically studied but never experimentally detected. This study presents an analysis of frozen intermediates containing alcohols lacking α-hydrogen atoms, preventing oxidation.
ISRAEL JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Physical
Aleksandr Y. Pereverzev, Corentin Rossi, Jana Roithova
Summary: The search for chemical structures responsible for diffuse interstellar bands remains a major challenge in astrochemistry, requiring experimental verification of structures obtained under laboratory conditions. In this study, we demonstrate the isomerization of the doubly charged polyaromatic hydrocarbon phenanthrene obtained through electron ionization. Our results show that the phenanthrene dication has a broad visible spectrum, making it unsuitable for diffuse interstellar band search. We also observe the isomerization of phenanthrene dication during the ionization process, leading to the detection of another C14H102+ isomer.
Article
Chemistry, Physical
Sreekanta Debnath, Alexander Schaefer, Karolina A. Haupa, Dmitry Strelnikov, Jana Roithova, Juraj Jasik, Sergei Lebedkin, Manfred M. Kappes
Summary: Helium tagging photodissociation action spectroscopy and laser-induced fluorescence spectroscopy in neon matrix were used to study the photophysics of electrosprayed rhodamine B cation at low temperatures. The experiments were conducted using He-TAG apparatus for helium tagging and Depo-II machine for LIF measurements. The resulting electronic spectra provide benchmarks for theoretical description of this organic dye.
Article
Chemistry, Multidisciplinary
Kananat Naksomboon, Enrique Gomez-Bengoa, Jaya Mehara, Jana Roithova, Edwin Otten, M. Angeles Fernandez-Ibanez
Summary: Pd-catalyzed C-H functionalization reactions of non-directed substrates have emerged as a promising alternative to the use of directing groups. A new type of S,O-ligand has been found to be highly efficient in promoting Pd-catalyzed C-H olefination reactions of non-directed arenes, although its role in the process was unclear. Through various mechanistic tools, it was discovered that C-H activation is the rate-determining step and the S,O-ligand triggers the formation of more reactive Pd cationic species, explaining the observed acceleration of the reaction. These findings provide important insights into the role of the S,O-ligand in promoting Pd-catalyzed C-H functionalization reactions.
Article
Chemistry, Multidisciplinary
Pieter J. Gilissen, Quentin Duez, Guilherme L. Tripodi, Magda M. J. Dekker, Jiangkun Ouyang, Kais Dhbaibi, Nicolas Vanthuyne, Jeanne Crassous, Jana Roithova, Johannes A. A. W. Elemans, Roeland J. M. Nolte
Summary: The kinetic enantio-recognition of chiral viologen guests by planar-chiral porphyrin cage compounds is determined by the planar chirality of the host and influenced by its size, but not the chirality of its substituents.
CHEMICAL COMMUNICATIONS
(2023)
