Article
Chemistry, Applied
Alexander Garay-Talero, Paola Acosta-Guzman, Diego Gamba-Sanchez
Summary: This manuscript presents a regioselective chlorination of arenes, yielding almost exclusively the monochlorinated product. It tolerates a wide range of functional groups and substituted aromatic rings, and demonstrates the utilization of chlorosulfonium salts as the chlorinating agent, avoiding the formation of organic byproducts.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Multidisciplinary Sciences
Yuanting Cai, Yuhui Hua, Zhengyu Lu, Qing Lan, Zuzhang Lin, Jiawei Fei, Zhixin Chen, Hong Zhang, Haiping Xia
Summary: This study demonstrates successful electrophilic aromatic substitution (EAS) reactions of molecules with Craig-Mobius aromaticity, such as osmapentalenes and fused osmapentalenes, which exhibit high reactivity to halogen electrophilic attack. Additionally, selective formation of a series of halogen-substituted metalla-aromatics via EAS reactions reveals a novel approach to otherwise elusive compounds. Density functional theory calculations were utilized to study the electronic effect on the regioselectivity of the EAS reactions.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2021)
Article
Biochemistry & Molecular Biology
Page M. Penner, James R. Green
Summary: The generation of E-carbonyl cations and their reactions with nucleophiles were achieved without the need for transition metal cation stabilization. The use of E-bromide dienoate or dienone starting materials and GaCl3 or InCl3 catalysis proved to be effective in this study. The viability of these cations was supported by DFT calculations.
Article
Chemistry, Applied
Sudip Guria, Constantin G. Daniliuc, Ulrich Hennecke
Summary: Enantioselective iodocycloetherifications can be achieved using sterically highly demanding BINOL-based phosphoric acid diesters as catalyst, requiring cocatalysis by triphenylphosphine selenide. Good to excellent enantioselectivities can be achieved for a broad range of substrates with low catalyst and cocatalyst loadings of 1 mol %. Triphenylphosphine selenide itself does not strongly impact diastereoselectivity, but improves reactivity and enhances enantioselectivity when combined with a BINOL-based phosphoric acid diester.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Review
Chemistry, Multidisciplinary
Jonathan Bock, Sudip Guria, Volker Wedek, Ulrich Hennecke
Summary: The dihalogenation of alkenes is a classic reaction in organic chemistry and typically exhibits anti-selectivity. Recent progress in reagent-controlled, enantioselective dihalogenation has been made, but challenges still remain in this transformation.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Partha Pratim Sen, Vishal Jyoti Roy, Sudipta Raha Roy
Summary: An atom economic method using noncovalent interactions to trigger paired electrolysis for bromination reactions is demonstrated. This mild and efficient electrochemical protocol allows the activation of C(sp(3))-Br bonds in organic-bromo derivatives, leading to the synthesis of aromatic compounds as well as useful byproducts.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Hugo Bloux, Amit Dahiya, Alexandra Hebert, Frederic Fabis, Franziska Schoenebeck, Thomas Cailly
Summary: Investigation of radio-iodination of arenes using ipso-electrophilic halogenation (IEH) from organosilane and organogermane precursors is performed. Discovery of a mild base mediated process enables radio-iodination in HFIP (1,1,1,3,3,3-hexafluoro-2-propanol) of aryl silane or germane, with germanes being more reactive. The clinical potential of arylgermanes as radio-iodination precursors is demonstrated through the labelling of [I-125]IMTO (iodometomidate) and [I-125]MIBG (meta-iodobenzylguanidine), providing an alternative to toxic precursors in radio-iododestannylation processes.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Biochemistry & Molecular Biology
Luis R. Domingo, Maria Jose Aurell, Mar Rios-Gutierrez
Summary: The reaction between N-phenyl iminoborane and benzaldehyde, presented by Liu et al., was investigated using Molecular Electron Density Theory (MEDT). The formation of a fused aromatic compound involves three consecutive reactions: the formation of a weak molecular complex between the reactants, an intramolecular electrophilic attack of the activated carbonyl carbon, and a formal 1,3-hydrogen shift. This domino reaction shows similarities to the Bronsted acid catalyzed Povarov reaction.
Article
Chemistry, Multidisciplinary
Huseyin Cem Kiliclar, Cagatay Altinkok, Gorkem Yilmaz, Yusuf Yagci
Summary: A novel visible light induced step-growth polymerization for forming poly(phenylene methylene) was developed, with the effect of different nucleophilic aromatic molecules on the polymerization investigated. The combination of step-growth polymerization with conventional free radical and free radical promoted cationic polymerizations through photoinduced chain-end activation was successfully demonstrated, resulting in highly fluorescent fibers of block copolymers. This versatile photoinduced step-growth polymerization process opens up a new pathway for a new generation of polycondensates and their combination with chain polymers that cannot be obtained by conventional methods.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Josefredo R. Pliego
Summary: The transition state for the substitution reaction involving one Br2 species with benzene as a model system exhibits high multiconfigurational character, requiring the use of the CR-CC(2,3) method for accurate description. The best functionals to evaluate the performance are M08-HX and B2GP-PLYP, with mean absolute deviation close to 3 kcal mol- 1.
COMPUTATIONAL AND THEORETICAL CHEMISTRY
(2021)
Article
Nanoscience & Nanotechnology
Shubhashish Shubhashish, Surani Wijenayake, Xueni Huang, Luisa F. Posada, Samantha Joy B. Rubio, Harshul S. Khanna, Destiny Dziengiel, Ali Mansour, Steven L. Suib
Summary: A straightforward synthesis method for highly mesoporous molybdenum oxide has been demonstrated using inverse micelles and molybdenum-oxo cluster formation. The synthesized catalyst is stable, crystalline, and phase pure MoO3, and shows 65 times higher activity than commercial parts. These materials exhibit excellent catalytic performance as solid acids in electrophilic substitution reactions.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Multidisciplinary
Ruizhi Guo, Ziqi Liu, Xiaodan Zhao
Summary: This study presents a convenient and efficient method to construct valuable P-chirogenic compounds through chiral selenide-catalyzed enantioselective electrophilic aromatic halogenation. The new chiral bifunctional selenide catalyst successfully converted various bis(2-hydroxyaryl) aryl phosphine oxides into chlorinated and brominated P-chirogenic compounds with good enantioselectivities. By adjusting the catalyst and solvent, the method could also prepare chiral alkyl diaryl phosphine oxides and diaryl phosphinates.
Article
Biochemistry & Molecular Biology
Pavel A. A. Zaikin, Ok Ton Dyan, Innokenty R. R. Elanov, Gennady I. I. Borodkin
Summary: The influence of liquid additives on the rate and selectivity of mechanochemical fluorination has been demonstrated, with ionic liquids shown to catalyze the reaction and improve the isolation of fluorinated products. A careful choice of additive results in high yields of fluorinated products and low E-factor for the overall process.
Article
Engineering, Environmental
Andrew W. Psoras, Seth W. McCoy, Keith P. Reber, Daniel L. McCurry, John D. Sivey
Summary: This study examines the influence of ipso substitution on the formation of trihalomethanes (THMs) during water chlorination. It confirms the conversion of C-Br bonds into C-Cl bonds for parabens and salicylates, resulting in the presence of brominated and nonhalogenated precursors, which generate polybrominated THMs. The THM molar yield and bromine incorporation were observed to be higher for brominated precursors compared to nonhalogenated precursors. The impact of ipso substitution on THM formation varies with the structure of the organic precursor.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Applied
Shubhashish Shubhashish, Sarah J. Karasik, Luisa F. Posada, Alireza S. Amin, Laura A. Achola, Nathaniel Nisly, William S. Willis, Steven L. Suib
Summary: This study presents a synthesis method for gold supported on metal oxides. The supported materials show higher crystallinity compared to unsupported systems. The gold support remains in its metallic state, while most of the other metals are observed to be in their oxide form. The gold supported catalysts exhibit enhanced activity and product selectivity in organic transformation reactions.
MICROPOROUS AND MESOPOROUS MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Viktor Paczelt, Raffael C. Wende, Peter R. Schreiner, Andre K. Eckhardt
Summary: In this study, the formation and spectroscopic characterization of glycine imine, the simplest imino acid, were reported using cryogenic matrix isolation IR and UV/Vis spectroscopy. Glycine imine was found to form after UV irradiation of 2-azidoacetic acid and could be interconverted between anti-(E,E)- and anti-(Z,Z)-conformations. In aqueous solution, glycine imine hydrolyzed to produce hydroxy glycine and hydrated glyoxylic acid. It was also observed that glycine imine could undergo self-reduction by oxidative decarboxylation chemistry when present in higher concentrations or in the presence of (FeSO4)-S-II as a reducing agent.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Artur Mardyukov, Raffael C. Wende, Peter R. Schreiner
Summary: 1,2-Ethenediols are key intermediates in prebiotic and interstellar syntheses of carbohydrates. In this study, we synthesized these enediols in the gas phase and trapped them in cryogenic argon matrices. Importantly, when subjected to photolysis at a wavelength of 180-254 nm, the enols rearrange into the simplest sugar, glycolaldehyde.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Alexander Seitz, Raffael C. C. Wende, Peter R. R. Schreiner
Summary: We describe the site-selective acetylation of partially protected monosaccharides using immobilized oligopeptide catalysts, synthesized via solid-phase peptide synthesis. The catalysts exhibit a reversed selectivity compared to N-methylimidazole and show high selectivity for various pyranosides. The catalysts demonstrate stability for multiple reaction cycles and can be easily reused after separation from the reaction solution. They can also be used in flow without any loss of reactivity and selectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Sebastian Schwan, Andreas J. Achazi, Ferdinand Ziese, Peter R. Schreiner, Kerstin Volz, Stefanie Dehnen, Simone Sanna, Doreen Mollenhauer
Summary: A systematic study of cluster dimers in adamantane-like molecular materials reveals that the binding energy between the dimers increases with the size of the core and the substituents. The cluster interactions can be classified as substituent-substituent-dominated or core-core-dominated. Understanding the interaction of the cluster dimers allows for an initial assessment of the interactions in the materials.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2023)
Article
Chemistry, Organic
Finn M. Wilming, Benito Marazzi, Paul P. Debes, Jonathan Becker, Peter R. Schreiner
Summary: We synthesized 14 2,2'-disubstituted 9,9'-bifluorenylenes to quantify London dispersion interactions between dispersion energy donors. Delta G(Z/E) was measured at 333 K using 1H NMR in seven solvents. Alkyl and aryl substituents showed a preference for the folded Z-isomer due to attractive London dispersion interactions, except for tert-butyl, which unexpectedly favored the unfolded E-isomer due to increased Pauli repulsion caused by close proximity of functional groups.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jan M. Schuemann, Lukas Ochmann, Jonathan Becker, Ahmet Altun, Ingolf Harden, Giovanni Bistoni, Peter R. Schreiner
Summary: We conducted an experimental study on a cyclooctatetraene-based molecular balance with disubstituted tert-butyl (tBu), adamantyl (Ad), and diamantyl (Dia) substituents in the 1,4-/1,6-positions. Our measurements, supported by solvation computations, showed that the more sterically crowded 1,6-isomer is always favored and that the free energy is insensitive to substituent size, regardless of the solvent.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
David King, Tatjana Sumanovac, Steven Murkli, Peter R. Schreiner, Marina Sekutor, Lyle Isaacs
Summary: We synthesized quaternary (di)cationic triamantane derivatives G1 and G3 by permethylating the corresponding primary ammonium ions G2 and G4. The complexation behaviors of G1-G4 with CB[7] and CB[8] were examined using H-1 NMR spectroscopy. CB[8] fully encapsulated G1-G4 while CB[7] formed inclusion complexes with G1, G2, and G4 but could not fully encapsulate the central hydrophobic core of G3. The geometries of the CB[n]-guest complexes were determined by analyzing complexation-induced changes in chemical shifts and confirmed using molecular modeling.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Weiyu Qian, Raffael C. Wende, Peter R. Schreiner, Artur Mardyukov
Summary: The interstellar candidate phosphorus mononitride PN, a metastable species, was generated through high-vacuum flash pyrolysis of (o-phenyldioxyl)phosphinoazide in cryogenic matrices. Although the PN stretching band was not directly detected because of its low infrared intensity and possible overlaps with other strong bands, o-benzoquinone, carbon monoxide, and cyclopentadienone as additional fragmentation products were clearly identified. Moreover, an elusive o-benzoquinone-PN complex formed when (o-phenyldioxyl)phosphinoazide was exposed to UV irradiation at lambda=254 nm. Its recombination to (o-phenyldioxyl)-lambda(5)-phosphinonitrile was observed upon irradiation with the light at lambda=523 nm, which demonstrates for the first time the reactivity of PN towards an organic molecule. Energy profile computations at the B3LYP/def2-TZVP density functional theory level reveal a concerted mechanism. To provide further evidence, UV/Vis spectra of the precursor and the irradiation products were recorded and agree well with time-dependent DFT computations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Weiyu Qian, Peter R. R. Schreiner, Artur Mardyukov
Summary: Carbenes and nitrenes are key intermediates in chemical processes and have received significant attention in synthetic chemistry, biochemistry, and materials science. Despite the well-characterized parent arsinidene (H-As), the reactivity of substituted arsinidenes has hindered their isolation and characterization. In this study, a triplet phenylarsinidene was prepared through the photolysis of phenylarsenic diazide and characterized using infrared and UV/vis spectroscopy. Doping matrices with molecular oxygen led to the formation of a previously unknown anti-dioxyphenylarsine, which further isomerized to a novel dioxophenylarsine upon 465 nm irradiation. Isotope-labeling experiments and computational methods supported the assigned structures.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Qigang Zhong, Artur Mardyukov, Ephrath Solel, Daniel Ebeling, Andre Schirmeisen, Peter R. Schreiner
Summary: On-surface synthesis is being recognized as the preferred method for generating and visualizing unconventional molecules. In this study, the structurally elusive cyclotriphosphazene (P3N3) was successfully synthesized on Cu(111) and Au(111) surfaces using molecular manipulation with unprecedented precision. The achieved atomic-level imaging revealed the planar D-3h-symmetric ring structure of cyclotriphosphazene.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Editorial Material
Chemistry, Multidisciplinary
Karsten Danielmeier, Peter R. Schreiner
Summary: The German Chemical Society (GDCh) has chosen "Rethinking Chemistry" as the guiding principle to address challenges related to climate change, loss of natural resources, and geopolitical conflicts. By encouraging scientists to approach chemistry from different perspectives, the GDCh aims to foster innovative and sustainable advancements in the field. This motto is also reflected in the upcoming GDCh Science Forum Chemistry (WiFo) 2023 and a dedicated Special Collection in Angewandte Chemie, showcasing the various aspects of Rethinking Chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Dennis Gerbig, Peter R. Schreiner
Summary: We report the successful preparation and identification of 1,2-dioxetanedione, a cyclic dimer of carbon dioxide. This compound was synthesized using a specific reaction method and its structure was confirmed through infrared spectroscopy and computational calculations. Furthermore, the successful isolation of this compound provides experimental evidence for its role as a high-energy intermediate in peroxyoxalate chemiluminescent systems.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Akkad Danho, Artur Mardyukov, Peter R. Schreiner
Summary: This study demonstrates the successful gas-phase synthesis of the previously unreported higher energy tautomer of propionic acid, prop-1-ene-1,1-diol. The enol was characterized using IR and UV/Vis spectroscopy along with density functional theory computations. Upon photolysis, the enol rearranges to propionic acid and methylketene.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Laura M. Grimm, Jeffry Setiadi, Boryslav Tkachenko, Peter R. Schreiner, Michael K. Gilson, Frank Biedermann
Summary: The thermodynamic parameters of host-guest binding can be used to describe, understand, and predict molecular recognition events in aqueous systems. This study focuses on the contributions of water to binding by studying binding thermodynamics for a series of host-guest systems. It is found that the enthalpic driving forces for binding increase at higher temperatures, and heat capacity changes appear to be a general feature of host-guest complex formation in water.
Article
Chemistry, Multidisciplinary
Akkad Danho, Artur Mardyukov, Peter R. Schreiner
Summary: The gas-phase synthesis of a higher energy tautomer, prop-1-ene-1,1-diol, of propionic acid is demonstrated in this study. The enol species is trapped in an argon matrix and characterized using IR and UV/Vis spectroscopy along with density functional theory calculations. Upon photolysis, the enol undergoes rearrangement to form propionic acid and methylketene.
CHEMICAL COMMUNICATIONS
(2023)
