Article
Chemistry, Multidisciplinary
Andreas Hess, Jan P. Prohaska, Sabrina B. Doerrich, Florian Trauner, Ferdinand H. Lutter, Sebastien Lemaire, Simon Wagschal, Konstantin Karaghiosoff, Paul Knochel
Summary: A new toluene-soluble reagent, sBu(2)Mg, has been developed for regioselective ortho-magnesiations of various N-arylated pyrazoles and 1,2,3-triazoles, as well as arenes with specific directing groups. The resulting diarylmagnesium reagents can be further functionalized and double ortho,ortho'-magnesiations can be achieved by repeating the magnesiation/electrophile trapping sequence, allowing for the preparation of valuable functionalized arenes.
Article
Chemistry, Applied
Paul Knochel, Kevin P. Cole
Summary: The tribute to Professor Victor Snieckus focuses on his significant contributions to the field of organic chemistry and directed ortho metalation technology.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2021)
Review
Biochemistry & Molecular Biology
Lucia Pazderova, Ece Zeynep Tuzun, Dmytro Bavol, Miroslava Litecka, Lukas Fojt, Bohumir Gruner
Summary: The cobalt bis(dicarbollide)(1(-)) anion plays a significant role in material science and medicine due to its unique properties and the availability of synthetic routes for easy modifications. The modification of the dicarbollide cage has been well-established for boron atom substitutions, but there has been limited progress on carbon vertex modifications. Recent developments in metalation reactions on C-H vertices have enabled direct and straightforward cage modifications, leading to new trends in the field. This review provides an overview of these methods and their applications in designing unconventional drugs.
Review
Chemistry, Organic
Lonwabo Ngodwana, Wanda Bout, Zoleka Nqaba, Teboho Motlokoa, Banele Vatsha
Summary: This tutorial review provides a brief overview of the access methodologies and limitations of resorcin[4]arenes, with a focus on the derivatization of the ortho-positions in the upper rim. It aims to inspire a renewed research interest in these derivatization strategies, enabling the synthesis of novel molecules and future applications.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Hao Wang, Lei Fu, Chunlin Zhou, Gang Li
Summary: The newly developed Pd-catalyzed meta-C-H bromination of aniline derivatives overcomes the ortho/para selectivity competition in electrophilic bromination, with the addition of acid additives crucial for reaction success. A broad range of substrates and benzoic acid derivatives with complex substitution patterns are applicable, with the potential for C-H chlorination under similar conditions.
Article
Chemistry, Inorganic & Nuclear
Martin Ravutsov, Georgi M. Dobrikov, Miroslav Dangalov, Rositsa Nikolova, Vladimir Dimitrov, Giuseppe Mazzeo, Giovanna Longhi, Sergio Abbate, Lorenzo Paoloni, Marco Fuse, Vincenzo Barone
Summary: A series of 1,2-disubstituted planar chiral ferrocenes were successfully synthesized through ortho-directed lithiation of chiral ferrocenesulfonamides and reaction with electrophilic reactants. The relative configurations of chemical groups were determined by NMR experiments and X-ray crystallography, while experimental ECD and VCD spectra were recorded and interpreted using quantum chemical computations.
Article
Polymer Science
Anastasiia Andriianova, Akhat Mustafin
Summary: The development of organic electronics has led to the emergence of new materials, with modification of known organic compounds being an important method. This study focuses on the modification of polyaniline (PANI) by introducing alkenyl substituents into the aromatic ring. (Co)polymers with aniline in different molar ratios were synthesized, and their solubility, thermal stability, humidity sensing, optical properties, and spectral characteristics were studied. The results show that the position shift of the double bond and the type of substituent have an impact on the properties of the polymers.
Article
Biochemistry & Molecular Biology
Jing Hu, Mengkang Gao, Yang Zhang, Yusui Wang, Zhenrui Qiao, Weiya Zhang, Qiang Wang, Lin Yan, Hai Qian
Summary: In this study, three series of new piperazine urea TRPV1 antagonists were designed, synthesized, and evaluated, among which compound 5ac showed excellent TRPV1 antagonistic activity, good bioavailability, and no hyperthermia side effects. The molecular docking study revealed that compound 5ac interacted well with the amino acid residues on rTRPV1 through hydrophobic interaction, making it an efficient TRPV1 antagonist and a potential candidate for analgesic drug development.
BIOORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Min Wen, William Erb, Florence Mongin, Yury S. Halauko, Oleg A. Ivashkevich, Vadim E. Matulis, Thierry Roisnel, Vincent Dorcet
Summary: This study reported a general synthetic method for the functionalization of N,N-dialkylferrocenyl sulfonamides. Additionally, the ligand behavior of new ferrocene phosphines in palladium-catalyzed coupling reactions was investigated.
Article
Chemistry, Organic
Tengda Si, Hun Young Kim, Kyungsoo Oh
Summary: The nitroso group acts as a traceless directing group in C-H functionalization and is ultimately removed after the reaction. The ability of o-NQ catalysts to oxidize N-alkylanilines without solvents and stoichiometric amounts of oxidants provides a new opportunity for developing telescoped catalyst systems without the need to handle hazardous N-nitroso compounds.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Yuanyuan Yue, Junli Chao, Zhiyue Wang, Yan Yang, Yaqing Ye, Chunying Sun, Xiaohui Guo, Jianming Liu
Summary: An efficient electrooxidative double C-H/C-H coupling of phenols with 3-phenylbenzothiophene has been developed under external oxidant- and catalyst-free conditions, enabling highly tunable access to benzothiophene derivatives. The reaction likely proceeds via the cross-coupling of the p-methoxylphenol radical and the 3-phenylbenzothiophene radical cation.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Physical
Andres Garcia-Dominguez, Pedro H. Helou de Oliveira, Gilian T. Thomas, Arnau R. Sugranyes, Guy C. Lloyd Jones
Summary: The study investigates the mechanism of anion-catalyzed C-H silylation by R3SiCF3 reagents using various experimental techniques. It reveals that a CF3-anionoid is the active intermediate, which undergoes arene deprotonation to generate ArSiMe3 and fluoroform. The kinetics of the process is directly controlled by the concentration ratio of [2]/[TMSCF3].
Article
Chemistry, Organic
Ran Wei, Andrew M. R. Hall, Richard Behrens, Mark S. Pritchard, Edward J. King, Guy C. Lloyd-Jones
Summary: The cover feature showcases the exploration and capture of fleeting information in rapid irreversible chemical reactions, with the application of NMR technology, researchers will reveal the mystery of reaction mechanisms.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Lucy van Dijk, Ruchuta Ardkhean, Mireia Sidera, Sedef Karabiyikoglu, Ozlem Sari, Timothy D. W. Claridge, Guy C. Lloyd-Jones, Robert S. Paton, Stephen P. Fletcher
Summary: The study proposes a catalytic cycle for the highly enantioselective Suzuki-Miyaura coupling of boronic acids and racemic allyl halides catalyzed by Rh(i), and reveals the reaction mechanism through kinetic isotope effects and experiments with stable substrates. The findings suggest that the high enantioselectivity is attributed to a common Rh complex formed from both allyl halide enantiomers.
Article
Chemistry, Organic
Ran Wei, Claire L. Dickson, Dusan Uhrin, Guy C. Lloyd-Jones
Summary: qNMR is a crucial tool in organic chemistry, used for reaction monitoring, mechanistic analysis, and purity determination. Knowledge of longitudinal relaxation time constants (T-1) is essential for establishing the correct acquisition rate for consecutive qNMR scans. The reported method for estimating T-1 is approximately 10 times faster than the conventional inversion recovery technique.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Hannah L. D. Hayes, Ran Wei, Michele Assante, Katherine J. Geogheghan, Na Jin, Simone Tomasi, Gary Noonan, Andrew G. Leach, Guy C. Lloyd-Jones
Summary: The study reveals the nuanced stability of boronic esters under basic aqueous-organic conditions, contrary to common assumption that esterification imparts greater stability compared to boronic acid. Additionally, hydrolysis of the ester to the boronic acid may be a dominant component of the overall protodeboronation process, especially when pH is close to the pKa of the boronic acid/ester.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Nicholas P. Taylor, Jorge A. Gonzalez, Gary S. Nichol, Andres Garcia-Dominguez, Andrew G. Leach, Guy C. Lloyd-Jones
Summary: The kinetics of quinuclidine displacement of BH3 from a wide range of Lewis base borane adducts have been measured, leading to the development of a nucleofugality scale. The utility of this scale has been demonstrated by correlating substituent parameters with hydrolyses rates of MIDA boronates, identifying compounds with unusual kinetic lability or stability to hydrolysis.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Claire N. Brodie, Timothy M. Boyd, Lia Sotorrios, David E. Ryan, Eimear Magee, Steven Huband, James S. Town, Guy C. Lloyd-Jones, David M. Haddleton, Stuart A. Macgregor, Andrew S. Weller
Summary: The study demonstrates the selective synthesis of N-methylpolyaminoborane using a specific air-tolerant precatalyst, revealing the reaction mechanism and key steps involved. This provides a theoretical basis for further research in this field.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Inorganic & Nuclear
Laurence R. Doyle, Martin R. Galpin, Samantha K. Furfari, Bengt E. Tegner, Antonio J. Martinez-Martinez, Adrian C. Whitwood, Scott A. Hicks, Guy C. Lloyd-Jones, Stuart A. Macgregor, Andrew S. Weller
Summary: The sequential solid/gas single-crystal to single-crystal reaction of [Rh(Cy2P(CH2)3PCy2)(COD)][BArF4] with H2 or D2 was studied using solid-state NMR spectroscopy and solution quenching techniques. The quantification of the reaction was done using a two-step JMAK model, revealing an inverse isotope effect for the second addition of H2 and the possibility of obtaining the structural solution of the alkane complex using D2. The results were supported by periodic DFT calculations.
Review
Chemistry, Multidisciplinary
Andres Garcia-Dominguez, Andrew G. Leach, Guy C. Lloyd-Jones
Summary: Reagent instability reduces the efficiency of chemical processes. This Account describes the mechanistic investigations into the decomposition of Suzuki-Miyaura cross-coupling of boronic acids/esters and the transfer of CF3 or CF2 from the Ruppert-Prakash reagent, TMSCF3. The research reveals different pathways and factors influencing the decomposition of the reagents.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Yael Ben-Tal, Guy C. Lloyd-Jones
Summary: The Ni/Ir-photocatalyzed coupling of ArBr with RBr was studied using in situ LED -F-19 NMR spectroscopy. Factors such as light, ArBr, Ni, and Ir were found to control the rate of ArBr consumption, while [(TMS)3SiH] and RBr independently controlled the product selectivity. The major resting state of nickel was identified as ArNiII(L)Br, and the complex undergoes Ir-photocatalyzed conversion to products in competition with the release of ArBr.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Kenichi Uno, Takanori Itoh, Hidenori Sato, Guy C. Lloyd-Jones, Yuya Orito
Summary: In this study, the leaching behavior of palladium on charcoal by aqueous HCl was observed using X-ray absorption spectroscopy. Pd(0) was not affected by the addition of HCl, while palladium oxide nanoparticles readily reacted with HCl to form [(PdCl4)-Cl-II](2-) ions, which mainly remained adsorbed on the charcoal surface and could only be detected at low concentrations in the solution. This finding provides new insights for controlling leaching behavior and the stable usage of palladium on charcoal in organic reactions.
Article
Multidisciplinary Sciences
George Peat, Patrick J. Boaler, Claire L. Dickson, Guy C. Lloyd-Jones, Dusan Uhrin
Summary: This study reports a new liquid-state NMR method for measuring the diffusion coefficient of pure compounds. By analyzing a narrow and intense singlet signal, the sensitivity is significantly increased, resulting in a time saving for measurements.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Andres Garcia-Dominguez, Nathan M. West, Robert T. Hembre, Guy C. Lloyd-Jones
Summary: The kinetics of the conversion of thiophenols into sulfenyl chlorides using N-chlorosuccinimide (NCS) has been investigated. The study reveals the important processes and factors involved in this reaction, as well as potential hazardous conditions and mitigation methods.
Article
Chemistry, Multidisciplinary
Rebecca L. Spicer, Helen M. O'Connor, Yael Ben-Tal, Hang Zhou, Patrick J. Boaler, Fraser C. Milne, Euan K. Brechin, Guy. C. Lloyd-Jones, Paul J. Lusby
Summary: Coordination cage catalysis is a strategy that utilizes a cage as an exogenous catalyst, rather than relying on the endogenous binding of substrates. The cage alters the properties of a cofactor guest, which then transfers reactivity to the bulk-phase to catalyze reactions.
Article
Chemistry, Organic
Nicholas P. Taylor, Jorge A. Gonzalez, Gary S. Nichol, Andres Garcia-Dominguez, Andrew G. Leach, Guy C. Lloyd-Jones
Summary: The kinetics of quinuclidine displacement of BH3 from a wide range of Lewis base borane adducts have been measured to develop a nucleofugality scale that can quantify and predict the leaving group ability of various Lewis bases. The study also explores the unusual kinetic stability or instability of MIDA boronates under hydrolysis conditions by correlating substituent parameters with hydrolysis rates.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
