Article
Chemistry, Inorganic & Nuclear
Li-Hui Hong, Wei-Jung Feng, Wei-Chih Chen, Yu-Chang Chang
Summary: We synthesized a palladium complex (1a) with two different P-donors and proved its effectiveness as a Pd(ii) precatalyst for carbon-phosphorus bond formation. The complex exhibited efficient catalytic activity for the Hirao coupling reaction under environmentally benign conditions. Mechanistic studies were conducted to investigate the generation of plausible Pd(0) active species. The use of bulky di(1-adamantyl)phosphine oxide as a preligand and less bulky di-p-tolylphosphine oxide as the substrate in the coupling reaction was also demonstrated.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Organic
Jinpeng Li, Changyu Huang, Daheng Wen, Qingshu Zheng, Bo Tu, Tao Tu
Summary: A nickel-catalyzed amination of aryl chlorides with diverse amides via C-N bond cleavage has been successfully achieved under mild conditions. The protocol offers a broad substrate scope with excellent functional group tolerance at a low catalyst loading, making it powerful for synthesizing various aromatic amines. Selective coupling of aryl chlorides to the amino fragments of amides rather than the carbonyl moieties expands the usage of inactive amides.
Article
Chemistry, Organic
Yaxu Liu, Vladislav A. Voloshkin, Thomas Scattolin, Min Peng, Kristof Van Hecke, Steven P. Nolan, Catherine S. J. Cazin
Summary: A synthetic procedure for preparing stable [Pd(NHC)Cl-2(DMS/THT)] pre-catalysts was reported, and their catalytic activity was studied in Buchwald-Hartwig and Suzuki-Miyaura reactions. The synthesized complexes exhibited higher catalytic activity and were considered as greener alternatives to classical PEPPSI type catalysts.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Xian Wei, Kun Wang, Weiwei Fang
Summary: In this study, an efficient catalytic system based on IPr-ligated chiral oxazoline palladacycles was developed for the alpha-arylation of aryl ketones with inactive aryl chlorides. The system tolerated a wide range of substrates at low catalyst loadings and resulted in good to excellent yields of the desired products.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Qinqin Xia, Shicheng Shi, Pengcheng Gao, Roger Lalancette, Roman Szostak, Michal Szostak
Summary: This study reports the synthesis, characterization, and reactivity of [(NHC)PdCl2(aniline)] complexes, which are highly active catalysts in various Suzuki-Miyaura reactions. The introduction of broadly available anilines as stabilizing ligands for well-defined Pd(II)-NHC catalysts has significant potential in fine-tuning challenging cross-coupling reactions. The commercialization of the parent catalyst [Pd(IPr)(AN)Cl-2] offers broad access for reaction screening and optimization.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Ryan Q. Tran, Long P. Dinh, Seth A. Jacoby, Nekoda W. Harris, William A. Swann, Savannah N. Williamson, Rebecca Y. Semsey, Larry Yet
Summary: 3-Aryl-1-phosphinoimidazo[1,5-a]pyridine ligands were synthesized through two different pathways using 2-aminomethylpyridine as the starting material, involving cyclization, iodination, and palladium-catalyzed cross-coupling phosphination reactions. These ligands were then evaluated in palladium-catalyzed sterically-hindered biaryl and heterobiaryl Suzuki-Miyaura cross-coupling reactions.
Article
Chemistry, Organic
Haiyao Ji, Han Cao, Guan Wang, Feifei Xing, Michal Szostak, Chengwei Liu
Summary: We have developed a general method for the direct decarbonylative thioetherification of carboxylic acids using stable nickel precatalysts. This approach allows for the direct use of carboxylic acids as aryl electrophiles and thiols as sulfide donors. The method has excellent functional group tolerance and broad substrate scope, making it a valuable tool for the synthesis of aryl sulfides. The synthetic potential of this method is demonstrated through the late-stage modification of pharmaceuticals utilizing carboxylic acid functional groups.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Shiyi Yang, Hengzhao Li, Xiang Yu, Jie An, Michal Szostak
Summary: A highly efficient protocol for the Suzuki-Miyaura cross-coupling of aryl fluorosulfonates using well-defined, air-and moisture-stable NHC-Pd(II) chloro dimers is presented. The reaction proceeds in excellent yields and with broad functional group tolerance using a very low loading of [Pd] in the presence of mild K3PO4 base under aqueous conditions. This operationally trivial protocol allows for the activation of C-O bond and is tolerant to various sensitive functional groups.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Mei-Ling Wang, Hui Xu, Han-Yuan Li, Biao Ma, Zhen-Yu Wang, Xing Wang, Hui-Xiong Dai
Summary: The Mizoroki-Heck reaction of unstrained aryl ketone with acrylate/styrene is achieved via palladium-catalyzed ligand-promoted C-C bond cleavage, providing good to excellent yields of the alkene product. Further applications in the late-stage olefination of drugs, natural products, and fragrance-derived aryl ketones demonstrate the synthetic utility of this protocol. By using ketone as both the directing group and the leaving group, 1,2-bifunctionalization is achieved through sequential ortho-C-H alkylation/ipso-Heck olefination.
Article
Multidisciplinary Sciences
Connor P. Delaney, Eva Lin, Qinan Huang, Isaac F. Yu, Guodong Rao, Lizhi Tao, Ana Jed, Serena M. Fantasia, Kurt A. Puentener, R. David Britt, John F. Hartwig
Summary: Copper complexes catalyze cross-coupling reactions through a newly discovered mechanism. The copper(II) complexes catalyze Ullmann coupling by synthesizing the C-O bond through concerted oxidative addition. This mechanism allows for high turnover numbers and the reactions can be performed in air.
Article
Chemistry, Inorganic & Nuclear
Raphael Bigler, Daniel Spiess, Joel Wellauer, Martin Binder, Victor Carre, Serena Fantasia
Summary: This study presents an efficient synthesis method for biaryl phosphine palladium(0) complexes with dvtms ligands, which exhibit good catalytic activity in Buchwald-Hartwig couplings for (hetero)aryl bromides and chlorides.
Article
Chemistry, Organic
Bo-Sheng Zhang, Wan-Yuan Jia, Yi-Ming Wang, Joao C. A. Oliveira, Svenja Warratz, Ze-Qiang Zhang, Xue-Ya Gou, Yong-Min Liang, Xi-Cun Wang, Zheng-Jun Quan, Lutz Ackermann
Summary: This report describes a method that utilizes a simple Pd/NBE catalytic system to achieve ortho functionalization of aryl iodide. By introducing dimethylamine and converting it to methyl quaternary ammonium salt, this method solves a long-standing problem in this field.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Kazuki Matsuo, Eiji Yamaguchi, Akichika Itoh
Summary: This study investigates the photoinduced C-X borylation reaction of aryl halides via the formation of a halogen-bonding (XB) complex using 2-naphthol as an XB acceptor. The method is chemoselective and tolerant to a broad range of functional groups, providing a concise route to corresponding boronate esters. Mechanistic studies reveal that the formation of the XB complex between aryl halide and naphthol acts as an electron donor-acceptor complex, generating aryl radicals through photoinduced electron transfer.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Alexander F. Schmidt, Anna A. Kurokhtina, Elizaveta Larina, Nadezhda A. Lagoda
Summary: Despite extensive studies on the reaction of Pd intermediates in the Suzuki-Miyaura reaction (SMR), direct evidence supporting the widely accepted assumptions regarding the activity of Pd hydroxo complexes is lacking. This study presents results on the reactivity of Pd-OH and/or Pd-OR-containing complexes in the transmetalation step under ligand-free turnover conditions. The catalytic involvement of specific Pd species was determined under real catalytic conditions by measuring the selectivity of competing reactions.
MOLECULAR CATALYSIS
(2023)
Article
Chemistry, Inorganic & Nuclear
Zhi-Mao Zhang, Yu-Ting Xu, Li-Xiong Shao
Summary: Three new N-heterocyclic carbene (NHC)-Pd(II) complexes using 5-phenyloxazole as the ancillary ligand were successfully synthesized in moderate to good yields. One of the complexes showed efficient catalytic activity in the Buchwald-Hartwig amination reaction, providing an alternative catalyst for the coupling of challenging yet cost-low aryl chlorides.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Paul Zaby, Jan Blasius, Anna K. Mueller, Steven P. Nolan, Oldamur Holloczki
Summary: The formation mechanism of metal-N-heterocyclic carbene (NHC) complexes from imidazolium salts in the presence of weak bases was investigated through theoretical methods. Quantum chemical calculations revealed that both sodium acetate and trimethylamine facilitate complex formation. Molecular dynamics simulations showed that the ionic nature of the [AuCl2](-) and imidazolium ions, as well as the sodium acetate base, keep these species associated in the reaction mixture through ion pairing. The neutral amine, however, remains mostly separated from the other reaction partners, making it a significantly less effective base.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Angeliki Giannoulis, Katrin Ackermann, Alexey Bogdanov, David B. B. Cordes, Catherine Higgins, Joshua Ward, Alexandra M. Z. Slawin, James E. E. Taylor, Bela E. E. Bode
Summary: Nitroxides, a unique class of persistent radicals, have a wide range of applications, from spin probes to polarizing agents. This study focuses on the synthesis of pyrroline-based nitroxide radicals and compares two possible synthetic routes for forming two key intermediates. The synthesized compounds were characterized using X-ray crystallography and their electronic communication was quantified using Continuous Wave Electron Paramagnetic Resonance (CW-EPR). This research expands the repertoire of mono- and bis-nitroxides and paves the way for studying quantum coherence effects and using them as polarizing agents.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Physical
Lin-jie Yang, Wenye Xuan, David Webster, Lethy Krishnan Jagadamma, Teng Li, David N. Miller, David B. Cordes, Alexandra M. Z. Slawin, Graham A. Turnbull, Ifor D. W. Samuel, Hsin-Yi Tiffany Chen, Philip Lightfoot, Matthew S. Dyer, Julia L. Payne
Summary: One of the advantages of organic-inorganic metal halides is their highly tuneable structures and properties, which are important for optimizing materials for photovoltaics and optoelectronic devices. In this study, bromine was included in a layered perovskite to induce a decrease in band gap and a structural transition. The inclusion of bromine also resulted in the formation of a new band in the electronic structure and a significant increase in mobility and/or carrier concentration. This work highlights the potential of molecular inclusion as a tool to tune the electronic properties of layered organic-inorganic perovskites.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Physical
Eimantas Duda, Subeesh Madayanad Suresh, David Hall, Sergey Bagnich, Rishabh Saxena, David B. Cordes, Alexandra M. Z. Slawin, David Beljonne, Yoann Olivier, Anna Koehler, Eli Zysman-Colman
Summary: This study introduces a molecular design that gradually increases the number of quasi-degenerate states to enhance the efficiency of thermally activated delayed fluorescence (TADF) using the oligomer approach. By selecting and arranging benzonitrile (BN) acceptors and amine donors, connected together via repetitive donor-acceptor units, the number of quasi-degenerate states is gradually increased. It is found that increasing the size of the oligomer enhances the rates of intersystem crossing and reverse intersystem crossing.
CHEMISTRY OF MATERIALS
(2023)
Editorial Material
Chemistry, Multidisciplinary
Paul Zaby, Jan Blasius, Anna K. K. Mueller, Steven P. P. Nolan, Oldamur Holloczki
Summary: In this issue, Oldamur Hollczki and co-workers from the Universities of Bonn, Ghent and Debrecen are featured on the cover. The image showcases the quest for an ionic base that can combine with the acidic proton of an imidazolium cation to form a carbene complex. For the full article, visit 10.1002/chem.202203636.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Sebastien G. Guillet, Ishfaq Ibni Hashim, Marek Belis, Kristof Van Hecke, Catherine S. J. Cazin, Steven. P. Nolan
Summary: A simple synthetic method for synthesizing various [Rh(acac)(CO)(NHC)] complexes is presented. In situ infrared monitoring provides valuable information on the reaction mechanism, including the identification of a crucial intermediate. Understanding the reaction mechanism has led to the discovery of novel pathways to commonly used congeners.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Sebastien G. Guillet, Aleksei A. Logvinov, Vladislav A. Voloshkin, Ekaterina A. Martynova, Steven P. Nolan
Summary: Researchers report a simple method for the synthesis of azetidines from 2-isoxasoline-3-carboxylates and alkenes, using [Au(cbz)(NHC)] complexes as photocatalysts. The reaction is applicable to a wide range of substrates. Mechanistic studies confirm the energy transfer pathway. This study further expands the potential application of gold catalysts in energy transfer chemistry and catalysis.
Article
Chemistry, Multidisciplinary
Tomas Matulaitis, Paloma L. dos Santos, Youichi Tsuchiya, David B. Cordes, Alexandra M. Z. Slawin, Chihaya Adachi, Ifor D. W. Samuel, Eli Zysman-Colman
Summary: Three new derivatives of 1,2,4,5-tetraphenylimidazole were synthesized and characterized. DMAC-TPI and PXZ-TPI showed low oscillator strength and low photoluminescence quantum yields, while PTZ-TPI exhibited room temperature phosphorescence by connecting a donor group to the N1 position.
Article
Chemistry, Inorganic & Nuclear
Lutao Zhang, Francesca A. Christie, Anna E. Tarcza, Helena G. Lancaster, Laurence J. Taylor, Michael Buhl, Olga L. Malkina, J. Derek Woollins, Cameron L. Carpenter-Warren, David B. Cordes, Alexandra M. Z. Slawin, Brian A. Chalmers, Petr Kilian
Summary: A series of peri-substituted acenaphthene-based phosphine selenoether bidentate ligands were synthesized and their properties in coordination with metals were investigated. The rigid ligands exhibited strong coupling effects and the coordination atoms were bridged by Lewis acidic motifs in the solid-state structures. Analysis of the NMR and X-ray diffraction data of the synthesized metal complexes provided insights into the interaction between the ligands and metals.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Stuart Burnett, Rochelle Ferns, David B. Cordes, Alexandra M. Z. Slawin, Tanja van Mourik, Andreas Stasch
Summary: This article reports on the different complexes obtained from the reactions of [(iPrDip)NacNac)Mg}(2)] with different reactants and reveals the structural characteristics of these complexes through experimental and computational studies.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Shiyi Yang, Xiang Yu, Yaxu Liu, Michele Tomasini, Lucia Caporaso, Albert Poater, Luigi Cavallo, Catherine S. J. Cazin, Steven P. Nolan, Michal Szostak
Summary: The Suzuki-Miyaura cross-coupling reaction enables the construction of biaryl ketones from inert amide bonds. However, the mechanism of C(acyl)-N bond oxidative addition and catalyst effect in this reaction remain poorly understood. This study investigates the use of [Pd(NHC)(sulfide)Cl-2] catalysts for amide N-C bond activation and presents the reaction development, kinetic studies, and reaction scope. DFT studies were also conducted to gain insight into the mechanism of C(acyl)-N bond oxidative addition and catalyst activation. The results suggest that [Pd(NHC)(sulfide)Cl-2] precatalysts could find application in C(acyl)-X bond activation in organic synthesis and catalysis.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Daniel J. Davidson, Fei Lu, Laura Faas, Daniel M. Dawson, Geoffrey P. Warren, Isabella Panovic, James R. D. Montgomery, Xiaoyan Ma, Boris G. Bosilkov, Alexandra M. Z. Slawin, Tomas Lebl, Afroditi Chatzifragkou, Steve Robinson, Sharon E. Ashbrook, Liz J. Shaw, Smilja Lambert, Isabella Van Damme, Leonardo D. Gomez, Dimitris Charalampopoulos, Nicholas J. Westwood
Summary: Cocoa pod husks, an underutilized resource in chocolate manufacturing, contain lignin with potential applications. An optimized extraction method led to high-quality lignin, allowing for further investigation of its structure and chemical transformation abilities. Preliminary analysis of other product streams from the husks was also conducted.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Crystallography
Saied M. Soliman, Ayman El-Faham, Assem Barakat, Alexandra M. Z. Slawin, John Derek Woollins, Morsy A. M. Abu-Youssef
Summary: Through X-ray crystallography, we synthesized and elucidated the structures of two IIB group complexes [Cd(DMPT)Cl-2] (6) and [Zn(DMPT)Cl-2] (7). Both complexes crystallized in the monoclinic crystal system, with different lattice parameters. Complex 6 exhibited a square pyramidal coordination environment, while complex 7 showed an intermediate between trigonal bipyramidal and square pyramidal coordination. Hirshfeld calculations revealed that hydrogen bonding interactions played a significant role in the supramolecular structure of both complexes.
Article
Chemistry, Multidisciplinary
Sylwia Ostrowska, Pierre Arnaut, David J. Liptrot, Catherine S. J. Cazin, Steven P. Nolan
Summary: The synthesis, isolation, and full characterization of a new copper complex [Cu(IPr)(OC(H)(CF3)(2))] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) are reported. This copper(I) complex is a versatile synthon capable of activating various X-H bonds including C-H, N-H, and S-H bonds. [Cu(IPr)(OC(H)(CF3)(2))] was investigated as a pre-catalyst in several catalytic reactions.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Alastair J. Nimmo, Jacqueline Bitai, Claire M. Young, Calum McLaughlin, Alexandra M. Z. Slawin, David B. Cordes, Andrew D. Smith
Summary: This study demonstrates an unusual reversible Michael addition reaction, using an isothiourea as a Lewis base catalyst, which produces stereoselective products. The basicity of the reaction conditions and the reactivity of the catalyst affect the selectivity of the products. By combining the reversible Michael addition with a crystallisation-induced diastereomer transformation, high yields and stereocontrol of the products can be achieved.
