Article
Chemistry, Organic
Xinyu Zhang, Jinli Zhang, Jie Chen, Banghua Zhou, Jian Zhang, Shunhong Chen, Jian Wu, Yaojia Jiang
Summary: An efficient and straightforward synthetic method for constructing trifluoromethyl 2H-thiophenes through [4 + 1] cycloaddition of enaminothiones with trifluoromethyl N-tosylhydrazones has been disclosed. The cycloaddition platforms were found to be compatible with a broad substrate scope and to show high regio- and stereo-selectivities under very mild reaction conditions such as room temperature, neutral media and low loading of catalyst.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Mathilde Rigoulet, David Vesseur, Karinne Miqueu, Didier Bourissou
Summary: This study reveals that Aryl trifluoromethyl diazomethanes can be decomposed to form alpha-CF3 substituted carbene complexes under the effect of certain gold(I) complexes. The bonding situation of these complexes is thoroughly evaluated, showing the influence of the aryl substituent and Au in stabilizing the electrophilic carbene center. Reactivity studies confirm the typical carbene-type behavior for one of the complexes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Bastiaan Kooij, Paul Varava, Farzaneh Fadaei-Tirani, Rosario Scopelliti, Dimitrios A. Pantazis, Gerard P. Van Trieste, David C. Powers, Kay Severin
Summary: In this study, we report the structural characterization of copper complexes with both bridging and terminal alkenylidene ligands. The complexes were obtained by irradiation of Cu-I complexes with N-heterocyclic diazoolefin ligands. The isolation and structural characterization of the complex with a terminal alkenylidene ligand were achieved through crystalline matrix isolation and in crystallo photolysis at low temperature.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Tsubasa Ito, Shingo Harada, Haruka Homma, Ayaka Okabe, Tetsuhiro Nemoto
Summary: Controlling extremely active species is a challenge in synthetic organic chemistry. Precious transition metals are commonly used to control the selectivity of carbene reactions. This study explored borane-catalyzed chemoselective dearomatizations using carbene-equivalent species and found that the activation model with a B-C bond is more promising. The study also demonstrated that the borane catalyst and terminal diazoamides enable dearomative spirocyclizations that cannot be achieved under metal catalysis.
Review
Chemistry, Inorganic & Nuclear
Feifei Li, Longqiang Xiao, Bang Li, Xingyi Hu, Lijian Liu
Summary: Carbene polymerization is a unique nonpetroleum-based polymerization pathway with broad applications. Over the past 20 years, significant progress has been made in the study of carbene polymerization, including efficient initiating systems, high molecular weight and stereoregular polycarbene, and controlled polymerization methods.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Shobhan Mondal, Ester Maria Di Tommaso, Berit Olofsson
Summary: Efficient protocols for accessing iodo-substituted diaryl and aryl(vinyl) sulfides have been developed using iodonium salts as reactive electrophilic arylation and vinylation reagents. The reactions take place under transition-metal-free conditions, employing odorless and convenient sulfur reagents. A wide variety of functional groups are tolerated in the S-diarylation, enabling the regioselective late-stage application of several heterocycles and drug molecules under mild reaction conditions. A novel S-difunctionalization pathway was discovered using vinyliodonium salts, which proceeds under additive-free reaction conditions and grants excellent stereoselectivity in the synthesis of aryl(vinyl) sulfides. A one-pot strategy combining transition-metal-free diarylation and subsequent reduction provided facile access to electron-rich thioanilines and a direct synthesis of a potential drug candidate derivative. The retained iodo group allows a wide array of further synthetic transformations. Mechanistic insights were elucidated by isolating the key intermediate, and the relevant energy profile was substantiated by DFT calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Katarzyna Orlowska, Klaudia Luczak, Piotr Krajewski, Joao V. Santiago, Katarzyna Rybicka-Jasinska, Dorota Gryko
Summary: Structurally diversified diazoalkanes can be activated under red light irradiation, producing reactive intermediates.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Mingshuai Zhang, Longkun Chen, Zhuoyuan Liu, Jiuzhong Huang, Fuchao Yu
Summary: Here, a straightforward method for obtaining 3a,7a-dihydroxy hexahydro-4H-indol-4-ones through Ru(III)-catalyzed alkenyl C(sp(2))-H bond functionalization/[3 + 2] annulation of enaminones with iodonium ylides is described. This protocol offers chemoselectivity, broad substrate scope, moderate to excellent yields, gram-scale synthesis, and mild reaction conditions. The resulting 3a,7a-dihydroxy hexahydro-4H-indol-4-one scaffolds can be easily further modified to 1H-pyrrol-3-ol carboxylate derivatives, showing potential applications in organic synthesis and medicinal chemistry.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Review
Chemistry, Applied
Parmjeet Kaur, Vikas Tyagi
Summary: This review highlights the recent progress in iron-catalyzed chemical and enzymatic carbene-transfer reactions using diazo compounds as carbene precursor, emphasizing the use of iron as a catalyst in organic synthesis.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Mingshuai Zhang, Longkun Chen, Zhuoyuan Liu, Jiuzhong Huang, Fuchao Yu
Summary: In this study, a straightforward and efficient method for the synthesis of 3a,7a-dihydroxy hexahydro-4H-indol-4-ones via Ru(iii)-catalyzed alkenyl C(sp(2))-H bond functionalization/[3 + 2] annulation of enaminones with iodonium ylides is described. The method exhibits chemoselectivity, broad substrate scope, moderate to excellent yields, gram-scale synthesis, and mild reaction conditions.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Minghui Qi, Muhammad Suleman, Yingxiao Wang, Ping Lu, Yanguang Wang
Summary: A series of isochromeno[3,4-d]imidazoles were synthesized in good yields via Rh(II)-catalyzed [3+2] annulation between 4-diazoisochroman-3-imines and oximes. This method involves the formation of rhodium carbene intermediates and elucidates the unique reactivity of oximes under Rh(II) catalysis. The reaction has the advantages of simple and mild reaction conditions, broad substrate diversity, and readily accessible starting materials and rhodium catalyst.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Feifei He, Rene M. Koenigs
Summary: In this study, the tris(pentafluorophenyl)borane-catalyzed reaction of carbazole heterocycles with aryldiazoacetates was reported. It was demonstrated that selective N-H or C-H functionalization could be achieved with good yields under different substrate conditions. The method showed promising application potential in 41 examples.
Article
Chemistry, Organic
Peng Zhao, Lingfeng Wang, Xiaoshuang Guo, Jiayi Chen, Yanbo Liu, Lei Wang, Yongmin Ma
Summary: An efficient photochemical strategy for the synthesis of fluorinated nitrogen-containing heterocycles from diazocarbonyl compounds is disclosed. This transformation involves the reaction of fluoroalkyl radicals with alpha-diazoketones under visible light. A wide range of N-heterocycles containing CF3 and perfluoroalkylated groups are successfully constructed in moderate to good yields. This photochemical strategy may serve as a valuable method for the synthesis of complex organofluorides via diazo/fluorine/radical chemistry.
Article
Chemistry, Organic
Gleb D. Titov, Grigory I. Antonychev, Mikhail S. Novikov, Alexander F. Khlebnikov, Elizaveta V. Rogacheva, Liudmila A. Kraeva, Nikolai V. Rostovskii
Summary: An orthogonal reactivity of diazo compounds toward azirine-2-carboxylic acids, switching with the reaction conditions, is demonstrated. A gold-catalyzed reaction is N-selective and produces 1,3-oxazin-6-ones, whereas a blue light activation leads to O-H insertion products, azirine-2-carboxylic esters. The observed chemodivergence is explained by the metal-bound and metal-free carbenes exhibiting different electronic properties in these reactions. In addition, a high antibacterial potential of the 1,3-oxazin-6-ones synthesized is shown.
Article
Chemistry, Organic
Rongxiang Chen, Guoyang Ma, Yawen Li, Jinju Zhang, Ran Xia, Kai-Kai Wang, Lantao Liu
Summary: This study describes a mild, convenient, and effective strategy using TBAI as a catalyst to catalyze the S-H and N-H insertion reactions of alpha-diazoesters with thiophenols and aromatic amines under metal-free conditions, providing a synthetic route for various thioethers and 2-amino-2-oxoacetates in moderate to excellent yields.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Russell R. A. Kitson, Christopher J. Moody
Summary: This paper reports the synthesis of a series of 19-substituted geldanamycin derivatives using optimized synthetic methods. These new compounds are of significant medicinal interest due to their significantly reduced toxicity compared to the unsubstituted counterparts previously evaluated in clinical trials.
Article
Biochemistry & Molecular Biology
Alessandra Garau, Giacomo Picci, Massimiliano Arca, Alexander J. Blake, Claudia Caltagirone, Greta De Filippo, Francesco Demartin, Francesco Isaia, Vito Lippolis, Anna Pintus, M. Andrea Scorciapino, M. Carla Aragoni
Summary: This study investigates the coordination chemistry of tetradentate pyridine-containing macrocycles towards Platinum Group metal ions Pd-II, Pt-II, and Rh-III, showing the structural characterization of the resulting complexes and the unique coordination environments of the ligands in different metal complexes. The study also utilizes Density Functional Theory calculations to determine the ground-state nature of a specific dinuclear Pt-II compound, providing insights into its electronic structure.
Article
Virology
Sarah Al-Beltagi, Cristian Alexandru Preda, Leah Goulding, Joe James, Juan Pu, Paul Skinner, Zhimin Jiang, Belinda Lei Wang, Jiayun Yang, Ashley C. Banyard, Kenneth H. Mellits, Pavel Gershkovich, Christopher J. Hayes, Jonathan Nguyen-Van-Tam, Ian H. Brown, Jinhua Liu, Kin-Chow Chang
Summary: Thapsigargin (TG) has shown potent antiviral activity against various respiratory viruses, including RSV, OC43, SARS-CoV-2, and influenza virus, with superior performance compared to existing drugs like remdesivir. This broad-spectrum inhibitor also demonstrated lasting antiviral effects and protection against lethal influenza virus challenge in mice.
Article
Oncology
Nurul A. Abdullah, Martyn Inman, Christopher J. Moody, Sarah J. Storr, Stewart G. Martin
Summary: A novel indolequinone compound IQ9 has shown significant inhibitory effects on breast cancer cells and enhanced radiosensitivity in triple-negative breast cancer cells. The study highlights the potential therapeutic value of indolequinones as radiosensitizers in breast cancer, targeting the thioredoxin system.
INVESTIGATIONAL NEW DRUGS
(2021)
Article
Chemistry, Multidisciplinary
Katie Ruffell, Frances R. Smith, Michael T. Green, Simon M. Nicolle, Martyn Inman, William Lewis, Christopher J. Hayes, Christopher J. Moody
Summary: Diazophosphonates, prepared from alpha-ketophosphonates by oxidation, are useful reagents in 1,3-dipolar cycloaddition reactions for synthesizing N-H pyrazoles. They possess stable properties compared to less stable diazoalkanes, and can migrate during the cycloaddition process.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Biochemical Research Methods
James R. Lloyd, Amy Hogan, Vasileios Paschalis, Jeddidiah Bellamy-Carter, Andrew Bottley, Graham B. Seymour, Christopher J. Hayes, Neil J. Oldham
Summary: Protein-ligand interactions are crucial for cell functionality, and carbene footprinting technique can provide valuable information about these interactions, such as binding sites and conformational changes. The application of carbene footprinting to the interaction between eIF4A helicase and hippuristanol has demonstrated the potential of this technique in studying protein-ligand interactions using labeling methods.
Article
Immunology
Sarah Al-Beltagi, Leah Goulding, Daniel K. E. Chang, Kenneth H. Mellits, Christopher J. Hayes, Pavel Gershkovich, Christopher M. Coleman, Kin-Chow Chang
Summary: The Delta variant of the COVID-19 virus has shown to have the highest replication rate and infectivity among the Alpha and Beta variants, and can boost the replication of co-infected viruses. Thapsigargin (TG) has proven to be highly effective in inhibiting all three variants, and can exhibit synergy in co-infections, effectively blocking viral replication.
Article
Biochemistry & Molecular Biology
Patricio Sanchez, Cristian O. Salas, Sebastian Gallardo-Fuentes, Alondra Villegas, Nicolas Veloso, Jessica Honores, Martyn Inman, Mauricio Isaacs, Renato Contreras, Christopher J. Moody, Jonathan Cisterna, Ivan Brito, Ricardo A. Tapia
Summary: This study describes the successful application of fragment-based drug discovery strategy to efficiently synthesize phenylamino or phenoxy-substituted benzofuran, benzoxazole, and benzothiazole quinones. Unusual results were observed in the regiochemistry of the reactions between bromoquinones and phenol/aniline during the final step of the synthesis. The findings indicate that the phenoxy quinone fragment led to compounds with increased cytotoxic activity against pancreatic cancer cells. Electrochemical properties of these quinones were also determined to understand their potential mechanism of action.
CHEMISTRY & BIODIVERSITY
(2022)
Article
Neurosciences
Anqi Yao, Sarah J. Storr, Martyn Inman, Lucy Barwell, Christopher J. Moody, Stewart G. Martin
Summary: This study investigated the therapeutic effects and underlying mechanisms of a novel Trx reductase (TrxR) inhibitor, IQ10, on brain cancer cells. The results showed that IQ10 inhibited the growth of brain cancer cells and sensitized them to radiation. It also exhibited potential anti-invasive and antimetastatic properties.
MOLECULAR NEUROBIOLOGY
(2022)
Article
Ecology
Christopher R. Cooney, Yichen He, Zoe K. Varley, Lara O. Nouri, Christopher J. A. Moody, Michael D. Jardine, Andras Liker, Tamas Szekely, Gavin H. Thomas
Summary: This study confirms the long-held belief that tropical bird species are more colorful than temperate species by analyzing a dataset of over 4,500 bird species.
NATURE ECOLOGY & EVOLUTION
(2022)
Article
Multidisciplinary Sciences
Yichen He, Zoe K. Varley, Lara O. Nouri, Christopher J. A. Moody, Michael D. Jardine, Steve Maddock, Gavin H. Thomas, Christopher R. Cooney
Summary: In this study, a deep learning-based image segmentation pipeline is developed to extract information on plumage UV reflectance from bird photographs. The results demonstrate that UV reflectance is widespread and phylogenetically conserved in passerine birds, and the light environment plays a significant role in promoting the evolution of UV plumage colouration.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Medicinal
Helen S. Summers, William Lewis, Huw E. L. Williams, Tracey D. Bradshaw, Christopher J. Moody, Malcolm F. G. Stevens
Summary: This study describes the design, synthesis, and characterization of novel analogues of temozolomide, a clinically used antitumor agent. The new compounds exhibit enhanced growth-inhibitory activity against various human tumor cell lines, including those that are resistant to temozolomide. Through rational design, the incorporation of a propargyl alkylating moiety and a thiazole ring as a replacement for a carboxamide has been achieved, resulting in potent and stable compounds. The findings suggest that further preclinical evaluation of the thiazole analogue is warranted.
EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Roberto Nolla-Saltiel, Ana M. Geer, Helen R. Sharpe, Cameron D. Huke, Laurence J. Taylor, Thomas G. Linford-Wood, Ashleigh James, Jamie Allen, William Lewis, Alexander J. Blake, Jonathan Mcmaster, Deborah L. Kays
Summary: This study reports the synthesis of ruthenium complexes with phosphinocarboxamide ligands and their use in forming metallacycles through halide abstraction/deprotonation reactions. The coordination and structure of these complexes were studied using X-ray diffraction and NMR spectroscopy, revealing the presence of intramolecular hydrogen bonding and rotational isomers in solution.
Article
Biochemistry & Molecular Biology
Maysaa M. Saleh, Duaa A. Abuarqoub, Alaa M. Hammad, Md Shahadat Hossan, Najneen Ahmed, Nazneen Aslam, Abdallah Y. Naser, Christopher J. Moody, Charles A. Laughton, Tracey D. Bradshaw
Summary: In this study, the anticancer activity of the bis-triazoles MS47 and MS49 was investigated, focusing on the human melanoma MDA-MB-435 cell line. MS47 showed selective cytotoxicity against melanoma and other cancer cell lines, with sub-micromolar GI(50) and LC50 values. Both MS47 and MS49 were found to inhibit cell growth and induce apoptosis in MDA-MB-435 cells, while MS47 also arrested cells at the G0/G1 phase. Furthermore, MS49 decreased Hsp90 protein expression in melanoma cells, indicating its binding to the G4-DNA promoter of the Hsp90 gene.
CURRENT ISSUES IN MOLECULAR BIOLOGY
(2023)
