Article
Chemistry, Inorganic & Nuclear
Nicholas R. Wiedmaier, Hartmut Schubert, Hermann A. Mayer, Lars Wesemann
Summary: The ruthenium carbene pincer complex 2 was synthesized by treating benzo annulated cycloheptatriene bisphosphine 1 with RuCl3. Addition of three equivalents of hydrogen to generate hydrogenated complex 4 was achieved through reaction at elevated temperatures. The dehydrogenation of complex 4 by heating in toluene solution formed ethane and alkyl complex 5 when reacted with ethylene.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Florian Leisinger, Dzmitry A. Miarzlou, Florian P. Seebeck
Summary: Molecular oxygen is a sustainable oxidation reagent with strong oxidizing properties and stability, ultimately forming water as the reaction product. The activation of O-2 can occur through various pathways, with enzymes typically forming metal-oxygen coordination complexes to facilitate the process. The formylglycine generating enzyme (FGE) demonstrates a unique strategy for activating O-2, involving binding of O-2 near, but not coordinated to, its catalytic copper atom.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Zhe Zhuang, Alastair N. Herron, Jin-Quan Yu
Summary: The development of C(sp(3))-H functionalizations of free carboxylic acids has provided a wide range of versatile reactions, enabling convenient synthesis of cyclic anhydrides using Mo(CO)(6) as a solid CO source and a bidentate ligand. Succinic anhydride products serve as versatile intermediates for introducing various functional groups at the beta position of parent acids, offering a divergent strategy for synthesizing carboxylic acids inaccessible by previous beta-C-H activation reactions. Furthermore, enantioselective carbonylation of free cyclopropanecarboxylic acids has been achieved using a chiral bidentate thioether ligand.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Zhe Zhuang, Shuang Liu, Jin-Tang Cheng, Kap-Sun Yeung, Jennifer X. Qiao, Nicholas A. Meanwell, Jin-Quan Yu
Summary: In this study, a novel C-H functionalization reaction was reported, which utilizes common protecting groups and practical oxidants for the lactamization of tosyl-protected aliphatic amides. The reaction was enabled by a specific ligand and shows mild reaction conditions, good scalability, and the use of convenient oxidants and protecting groups. Further derivatization of the beta-lactam products allows the synthesis of various biologically significant compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Bo Yang, Jihui Gao, Xingfa Tan, Yicong Ge, Chuan He
Summary: A new type of chiral silyl ligand is developed, enabling the first iridium-catalyzed atroposelective intermolecular C-H silylation reaction of 2-arylisoquinolines. This protocol offers mild reaction conditions, high atom economy, and remarkable yield with excellent stereoselectivity, delivering enantioenriched axially chiral silane platform molecules with facile convertibility. The success of this unprecedented transformation relies on a novel chiral PSiSi-ligand, which facilitates the intermolecular C-H silylation process with perfect chem-, regio-, and stereo-control via a multi-coordinated silyl iridium complex.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Qian Gao, Senmiao Xu
Summary: We report a carbamate-directed iridium-catalyzed asymmetric beta-C(sp(3))-H borylation of strained (hetero)cycloalkanes. Densely functionalized cyclopropanols were obtained in good enantioselectivities via desymmetrization and kinetic resolution. Site-selective C(sp(3))-H borylation of methine groups provided alpha-borylated (hetero)cycloalkanols in moderate to good yields. The synthetic utility of the method was demonstrated in a gram-scale synthesis and various downstream transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Quan Gou, Qianqiong Chen, Qujian Tan, Minghong Zhu, Huisheng Huang, Mengjiao Deng, Wei Yi, Shuhua He
Summary: In this study, a first catalytic protocol for nickel-catalyzed ortho or para position difluoromethylation of various aromatic amines was developed with the assistance of a bidentate phosphine ligand. This method offers an invaluable synthesis means to construct extensive p-difluoromethylated products and difluorooxindole derivatives with significant functional fragments. The gram-scale reaction, broad substrate scope, excellent functional-group compatibility, late-stage difluoromethylation of pesticides, and even formal synthesis of HDAC6 inhibitors further demonstrate the usefulness of this method.
Article
Chemistry, Multidisciplinary
Eva Sanchez-Perez, Fernando Santos-Escobar, J. Felix Gutierrez-Corona, Kazimierz Wrobel, Katarzyna Wrobel, Oracio Serrano
Summary: This work describes a serendipitous self-assembly synthesis of non-symmetrical CNN-platinacycle pincer complexes, with an early formation and detection of hydride species. The synthesis involves a formal C-H bond activation and an earlier C-N bond formation, achieved via C-Br bond excision. Experimental results show that the nature of the Pt(II)-starting material does not significantly affect the reaction pathway, and the best yields are achieved using stoichiometric amounts of K2PtCl4, appropriate Schiff base ligand and aniline at 70 degrees C for three days.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Biochemistry & Molecular Biology
Ronja Jordan, Doris Kunz
Summary: The coordination chemistry of an electron-rich macrocyclic CNC pincer-ligand was studied using NMR spectroscopy and X-ray crystal structure analysis. It was found that the ligand exhibited bridging coordination with lithium, facial coordination with potassium, and C-H activation with metal complexes.
Article
Chemistry, Multidisciplinary
Chen-Hui Yuan, Xiao-Xia Wang, Lei Jiao
Summary: We developed sulfoxide-2-hydroxypridine (SOHP) ligands that showed great efficiency in the Pd-catalyzed C(sp(2))-H activation. In this study, we presented an efficient asymmetric Pd-II/SOHP-catalyzed beta-C(sp(3))-H arylation of aliphatic tertiary amides, where the SOHP ligand played a crucial role in the stereoselective C-H deprotonation-metalation step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Ryohei Kawazu, Takeru Torigoe, Yoichiro Kuninobu
Summary: New ligands have been discovered for iridium-catalyzed C(sp(3))-H borylation of aliphatic compounds. A phenanthroline-based NNSi pincer ligand has shown excellent performance and enables efficient conversion of aliphatic compounds to borylated products using an Ir/NNSi pincer catalyst system.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Philipp M. Rutz, Joerg Grunenberg, Christian Kleeberg
Summary: A diamino dialkoyx diborane(4) with additional P donor moieties was obtained by the reaction of a copper(I) boryl complex and a borane. This compound reacted with copper(I) tert-butoxide and [Pt(P(iPr)3)2] to form novel bis-mu-boryl di-copper(I) complex and trans-bis-boryl platinum(II) complex, respectively.
Article
Chemistry, Inorganic & Nuclear
Leah Webster, Tobias Kramer, F. Mark Chadwick
Summary: This article demonstrates the attachment of the "POCOP" pincer ligand to titanium in Ti(III) and Ti(IV) complexes for the first time, highlighting its significance in reactions.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Physical
Jiayu Mo, Antonis M. Messinis, Joao C. A. Oliveira, Serhiy Demeshko, Franc Meyer, Lutz Ackermann
Summary: The C-H/C-C functionalization with oxymethylated bicyclopropylidenes using an iron catalyst under external oxidant-free conditions led to the synthesis of various pharmacologically active compounds. The mechanism involving C-C cleavage via beta-C elimination was supported by mechanistic studies, and a rare monoselective C-F/C-H bond functionalization of trifluoromethylarene was observed.
Article
Chemistry, Physical
Wenjun Yang, Ivan Yu. Chernyshov, Manuela Weber, Evgeny A. Pidko, Georgy A. Filonenko
Summary: In this study, a Mn(I) pincer complex that promotes site-controlled transposition of olefins was reported. By suppressing the N-H functionality within the complex through alkylation, a wide range of allylarenes can be efficiently converted to higher-value 1-propenybenzenes with excellent stereoselectivities. The complex also retains the reactivity towards a single positional isomerization for long-chain alkenes.
Article
Chemistry, Physical
Greg Brewer, Raymond J. Butcher, Peter Zavalij
Article
Chemistry, Multidisciplinary
Steven Murkli, Jared Klemm, David King, Peter Y. Zavalij, Lyle Isaacs
CHEMISTRY-A EUROPEAN JOURNAL
(2020)
Article
Chemistry, Organic
Xiaoyong Lu, Sandra A. Zebaze Ndendjio, Peter Y. Zavalij, Lyle Isaacs
Article
Chemistry, Inorganic & Nuclear
Peter Y. Zavalij, Ai-Min Li, Bryan W. Eichhorn
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
(2020)
Article
Multidisciplinary Sciences
Y. G. Liang, S. Lee, H. S. Yu, H. R. Zhang, Y. J. Liang, P. Y. Zavalij, X. Chen, R. D. James, L. A. Bendersky, A. Davydov, X. H. Zhang, I Takeuchi
NATURE COMMUNICATIONS
(2020)
Article
Chemistry, Physical
Mark A. Wallace, Peter Y. Zavalij, Lawrence R. Sita
Article
Chemistry, Multidisciplinary
Xiaoxi Lin, Arkadi Vigalok, Andrei N. Vedernikov
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Nanoscience & Nanotechnology
A. R. Kytsya, L. I. Bazylyak, I. Yu. Zavaliy, Yu. V. Verbovytskyy, P. Zavalij
Summary: Bimetallic Ni-Cu nanoparticles with different (Ni/Cu) ratio were synthesized through a fast and simple reduction process in water/ethylene glycol solutions. The nanoparticles showed polydisperse sizes within 20-70 nm, with the particle diameter slightly depending on the Ni/Cu ratio. Additionally, XRD and EDX analyses revealed changes in lattice parameters and core-shell structure, respectively.
APPLIED NANOSCIENCE
(2022)
Article
Chemistry, Inorganic & Nuclear
A. P. Prakasham, Arkadi Vigalok, Andrei N. Vedernikov
Summary: A series of Pd(II) aryl complexes with a PNO-type pincer ligand bearing a weakly coordinated benzofuran side arm has been studied. The Pd-O distances were found to depend on the aromatic group at the Pd center. Changing the electron density at the metal can affect these interactions and be utilized in chemical reactions.
Article
Engineering, Environmental
Matthew B. Leonard, Tianyu Li, Morgan J. Kramer, Shannon M. McDonnell, Andrei N. Vedernikov, Efrain E. Rodriguez
Summary: The research suggests that CeO2 is the most reactive material, with a surface area normalized rate constant 3-4.6 times larger than TiO2 and CexTi1_xO2 series. Additionally, the nature of the cation is found to be less significant in the reactivity of methyl paraoxon on these MMOs compared to factors like crystal structure type.
JOURNAL OF HAZARDOUS MATERIALS
(2022)
Article
Chemistry, Organic
Michael Hitt, Andrei N. Vedernikov
Summary: N-Trifluoroacetoxyquinuclidinium trifluoroacetate was prepared in situ and used as a reagent for the high-yielding oxidative trifluoroacetoxylation of benzylic C-H bonds. The reaction showed selectivity for 2 degrees benzylic C-H bonds and suggested a hydrogen-atom transfer mechanism for alkylbenzenes.
Article
Chemistry, Inorganic & Nuclear
Jiaheng Ruan, Daoyong Wang, Morgan J. Kramer, Peter Y. Zavalij, Andrei N. Vedernikov
Summary: In this study, two sulfonated CNN-pincer ligands were used to explore the oxidative functionalization of the PtII-Me bond in derived complexes, with O2 and H2O2 as oxidants. Different high-valent platinum complexes were produced depending on the oxidant used, showing the importance of ligand structure on the reaction outcome.
Article
Chemistry, Organic
Michael Hitt, Andrew Norris, Andrei N. N. Vedernikov
Summary: A series of N-aroyloxyquinuclidinium salts were synthesized and used as reagents for efficient three-component Ritter-Mumm-type oxidative C-H imidation reactions. The benzylic C-H bonds of 1 & DEG; and 2 & DEG; substituents were used as limiting reagents, with nitriles as the source of imide nitrogen under photocatalytic conditions. These reagents also showed slightly lower reactivity towards cycloalkanes.
Article
Chemistry, Multidisciplinary
Shrinwantu Pal, Kyoko Nozaki, Andrei N. Vedernikov, Jennifer A. Love
Summary: The study demonstrates complete deuteration of Pt-CH3 fragments through a metal-ligand cooperative mechanism, resulting in the synthesis of (dp)Pt-II(CD3)(2). Experimental results show that the DPK ligand enables Pt-CH3 deuteration, while other model ligands lead to non-rate-limiting reductive coupling reactions.
Article
Chemistry, Inorganic & Nuclear
Morgan Kramer, David Watts, Andrei N. Vedernikov