Article
Chemistry, Organic
Yuji Nishiura, Kevin J. Gonzalez, Alexander Q. Cusumano, Brian M. Stoltz
Summary: Spirocyclic scaffolds are important motifs that can have favorable effects on pharmaceutical compounds. This study reports a high-yielding and enantioselective method for synthesizing chiral spirocyclic heterocycles.
Article
Chemistry, Multidisciplinary
Tomoya Miura, Kohei Hagiwara, Takayuki Nakamuro, Yuuya Nagata, Naoki Oku, Masahiro Murakami
Summary: A method for the synthesis of 3,5-disubstituted-1,2,4-triazoles from nitriles and 5-aryltetrazoles is described. The reaction involves ring-chain tautomerization, denitrogenation, and 1,3-dipolar cycloaddition to achieve regioselective formation of the desired triazoles.
Article
Chemistry, Multidisciplinary
Run-Kai Fang, Zheng-Chun Yin, Jun-Shen Chen, Guan-Wu Wang
Summary: A convenient and efficient [3 + 2] cycloaddition reaction of alkenes and alkynes with the in situ generated nitrile oxides from aldoximes in the presence of NaCl, Oxone and Na2CO3 has been developed to afford a series of isoxazoles and isoxazolines at room temperature in yields up to 85% and 86%, respectively. The current methodology exhibits a wide substrate scope, (hetero)aromatic and aliphatic aldoximes, alkenes including acrylate esters, acrylonitrile, chalcone, styrene, N-methylmaleimide and [60]fullerene, phenylacetylene, and alkynes containing CH2OH, SiMe3, COCH3 or CO2CH3 group can be employed. The present protocol features good functional group tolerance, short reaction time, mild reaction conditions and high atom economy, providing an efficient and environmentally friendly access to isoxazoles and isoxazolines.
GREEN CHEMISTRY LETTERS AND REVIEWS
(2022)
Article
Chemistry, Organic
Arturs Sperga, Armands Kazia, Janis Veliks
Summary: This study demonstrates a novel method for synthesizing five-membered rings using fluoromethylene transfer chemistry to produce fluorinated products of high value. The approach involves a one-step synthesis, utilizing one-fluorine-one-carbon modification of a substrate to access monofluorinated five-membered rings.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Pallab Karjee, Santu Mandal, Bijoy Debnath, Nirali Namdev, Tharmalingam Punniyamurthy
Summary: Efficient annulation of in situ formed azaoxyallyl cations using diaziridines has been achieved at room temperature with the aid of a base, leading to the formation of 1,2,4-triazines. The practical advantages of this reaction include its broad substrate scope, scalability, high tolerance towards functional groups, and the absence of transition-metal catalysts.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Tofik Ahmed Shifa, Khabib Yusupov, Getachew Solomon, Alessandro Gradone, Raffaello Mazzaro, Elti Cattaruzza, Alberto Vomiero
Summary: This study highlights the significant role of Sn in accelerating the electron transfer kinetics of Ni5P4 nanosheets in the oxygen evolution reaction (OER). The presence of electrochemically induced Ni-Sn oxides near phosphides was found to be responsible for the observed catalytic activity. Experimental and theoretical calculations supported these findings, paving the way for practical implementation of hydrogen production through water splitting and other catalytic reactions.
Article
Metallurgy & Metallurgical Engineering
D. Pukazhselvan, K. S. Sandhya, Devaraj Ramasamy, Aliaksandr Shaula, Igor Bdikin, Duncan Paul Fagg
Summary: This study found that zirconia additive can chemically interact with MgH2, forming active in-situ catalysts to improve hydrogen storage performance.
JOURNAL OF MAGNESIUM AND ALLOYS
(2022)
Article
Chemistry, Organic
Lu-Nan Zhou, Fang-Fang Feng, Chi Wai Cheung, Jun-An Ma
Summary: The unified construction of cyano-substituted 1,2,4-triazoles, especially the 5-cyano counterparts, is still limited. A three-component method using readily available materials has been described to access a wide range of 1-aryl 5-cyano-1,2,4-triazoles, showing potential applications in the synthesis of structurally diverse bioactive compounds and novel bidentate ligands for asymmetric catalysis.
Article
Chemistry, Organic
Cornelius Gaertner, Christoph Schneider
Summary: In this study, an asymmetric cooperative process is reported for the enantioselective 1,6-addition of fi-ketoesters to in situ generated para-quinone methides using chiral Pd-aqua complexes as mixed Bronsted acid-base catalysts. The reaction exhibits excellent yields, outstanding enantiocontrol, and good diastereoselectivity across a wide range of substrates. The utility of this reaction is demonstrated through facile scale up and subsequent complexity-increasing modifications.
Article
Chemistry, Multidisciplinary
Oleg Grossmann, Rajat Maji, Miles H. Aukland, Sunggi Lee, Benjamin List
Summary: Strong and confined IDPi catalysts enable highly enantioselective substitutions of cyclic, aliphatic hemiaminal ethers with enol silanes, giving access to 2-substituted pyrrolidines, piperidines, and azepanes with high enantioselectivities. The method exhibits broad tolerance towards various enol silane nucleophiles. Mechanistic studies suggest the involvement of non-stabilized, cyclic N-(exo-acyl)iminium ions with the confined chiral counteranion as intermediates, while computational studies provide transition states that account for the observed enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Materials Science, Multidisciplinary
E. Piskorska-Hommel, M. J. Winiarski, M. Kurnatowska
Summary: The presence of mixed-valence state Ce4+/Ce3+ in Ce0.7Yb0.2Pd0.1O2-delta was confirmed, and the reduction activity temperature of Ce was found to be significantly lower than previously reported, with Yb and Pd ions enhancing oxygen vacancy formation.
MATERIALS CHEMISTRY AND PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Huaping Xu, Xiaoyu Kong, Mengjie Cen, Ze-Feng Xu, Shengguo Duan, Chuan-Ying Li
Summary: In this study, the regioselective synthesis of dihydropyrroles was achieved through a cascade reaction. By employing a specific catalyst, the desired product was efficiently synthesized. This method has great potential for the synthesis of compounds with different ring systems.
CHEMICAL COMMUNICATIONS
(2022)
Article
Agricultural Engineering
Dong Hui Liang, Yongyou Hu, Jianhua Cheng, Yuancai Chen
Summary: Microbial activity plays a decisive role in the removal of sulfamethoxazole and nitrogen-N, while the catalytic character of sediment enhances the degradation of sulfamethoxazole. A possible degradation pathway was proposed based on the intermediate products, and the environmental toxicity of each intermediate was calculated using the ECOSAR program.
BIORESOURCE TECHNOLOGY
(2021)
Article
Chemistry, Organic
Cai-Mei Nong, Si-Ning Lv, Wei-Min Shi, Cui Liang, Gui-Fa Su, Dong-Liang Mo
Summary: A series of 1,2,4-oxadiazoline derivatives were successfully synthesized through a deoxygenative cyclization reaction of N-vinyl-alpha,beta-unsaturated nitrones and hydroxamoyl chlorides. The reaction proceeded through double additions of nitrile oxides, sequential elimination, and intramolecular cyclization. Additionally, 1,2,5-oxadiazolines were also obtained in specific solvents. The prepared 1,2,4-oxadiazolines could be easily transformed into polysubstituted pyrroles under thermal conditions.
Article
Chemistry, Multidisciplinary
Mei-Mei Li, Hui Huang, Wanrong Tian, Yiru Pu, Chaozheng Zhang, Jirui Yang, Qing Ren, Feiyan Tao, Yun Deng, Jun Lu
Summary: A highly efficient potassium carbonate-mediated [3 + 2] cycloaddition reaction has been developed for the synthesis of multi-substituted pyrazoles using hydrazonoyl chlorides and cinnamic aldehydes. This protocol offers a broad substrate coverage, good functional group tolerance, wide scalability, operational simplicity, and convenient construction of pyrazole scaffolds.
Article
Chemistry, Multidisciplinary
Marie-Claire Giel, Christopher J. Smedley, Emily R. R. Mackie, Taijie Guo, Jiajia Dong, Tatiana P. Soares da Costa, John E. Moses
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Multidisciplinary
Christopher J. Smedley, Gencheng Li, Andrew S. Barrow, Timothy L. Gialelis, Marie-Claire Giel, Alessandra Ottonello, Yunfei Cheng, Seiya Kitamura, Dennis W. Wolan, K. Barry Sharpless, John E. Moses
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Physical
Max Winslow, Warren B. Cross, David Robinson
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2020)
Article
Chemistry, Organic
Pallavi Sharma, M. R. Ranga Prabhath, Derek Wong, Maame Adjoa Ampem-Lassen, Shreesha Bhat, Luke Williams, Teresa G. Carvalho
Summary: In this study, a novel spiroannulation reaction of exoimines with 1,3-dipoles was demonstrated for the first time, leading to the synthesis of 3D spirocycles with a secondary amine in the spiro-ring. This synthetic method provides access to previously unexplored heterospirocyclic cores, with potential applications in the discovery of functional molecules for medicinal and materials science. The discovery of a new class of heterospirocycles with antimalarial activity against P. falciparum further confirms the potential of this approach.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Asia Al-jabiry, Martin Palmer, James Langridge, Jeddidiah Bellamy-Carter, David Robinson, Neil J. Oldham
Summary: Native mass spectrometry is an important tool in structural biology, allowing researchers to study the nature of higher protein structure in the vacuum of the mass spectrometer. By combining protein chemical modification and CIU, the stabilising role of interactions in gas-phase protein structure can be elucidated.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
David Robinson, Saleh S. Alarfaji, Jonathan D. Hirst
Summary: This study investigates the oscillator strengths of benzene, toluene, aniline, fluorobenzene, and phenol, finding that a simple pseudo-diabatization approach can improve accuracy, especially in cases of weak to moderate coupling.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Chemistry, Multidisciplinary
Christopher J. Smedley, Joshua A. Homer, Timothy L. Gialelis, Andrew S. Barrow, Rebecca A. Koelln, John E. Moses
Summary: Accelerated SuFEx click chemistry (ASCC) is an improved method for efficient and catalytic coupling of aryl and alkyl alcohols with various SuFExable hubs. The powerful combination of BTMG and HMDS reagents allows for lower catalyst loadings, providing a scalable method that is safe, efficient, and practical for modular synthesis. ASSC expands the accessibility of SuFEx products and will have significant applications in organic synthesis, medicinal chemistry, chemical biology, and materials science.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Sharad S. Amin, Jamie M. Cameron, Max Winslow, E. Stephen Davies, Stephen P. Argent, David Robinson, Graham N. Newton
Summary: A mixed-addenda polyoxometalate cluster containing both W and Mo centers was synthesized under acidic conditions. The structure and electronic effects of metal substitution were studied and compared to its tungsten-only analogue.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Anna M. Tsouri, David Robinson
Summary: The production and reactions of singlet oxygen pose a major challenge to the safe storage and transportation of food. While experimental studies on the reactions between singlet oxygen and cholesterol have been conducted, a detailed understanding of the reaction mechanisms and intermediates involved is still lacking. In this study, density functional theory was employed to investigate the reaction pathways and transition states of singlet oxygen and cholesterol. Epoxide-like intermediates were identified, shedding light on the formation of 5,6-epoxide derivatives of cholesterol, which are indicative of liver function.
Article
Chemistry, Multidisciplinary
Sharad S. Amin, Kieran D. Jones, Alexander J. Kibler, Heather A. Damian, Jamie M. Cameron, Kevin S. Butler, Stephen P. Argent, Max Winslow, David Robinson, Nicholas J. Mitchell, Hon Wai Lam, Graham N. Newton
Summary: Here, we report the synthesis and characterization of a new class of hybrid Wells-Dawson polyoxometalate (POM) with a diphosphoryl group (P2O6X). Modifying the bridging unit X impacts the redox potentials of the POM. The easy preparation of a range of alpha-functionalized diphosphonic acids (X=(CRR2)-R-1) provides possibilities for diverse functionalized hybrid POMs. Compared to existing phosphonate hybrid Wells-Dawson POMs, diphosphoryl-substituted POMs offer a wider tunable redox window and enhanced hydrolytic stability. This study provides a basis for the rational design and synthesis of next-generation hybrid Wells-Dawson POMs.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Christopher J. Smedley, Marie-Claire Giel, Thomas Fallon, John E. Moses
Summary: In this study, we present a method for synthesizing a stable precursor to ethene-1,1-disulfonyl difluoride (EDSF) and demonstrate its use in the preparation of various functionalized 4-membered ring carbocycles. These carbocycles are important structural motifs found in bioactive natural products and pharmaceutically relevant small molecules. We also show that the novel cyclobutene cores can be diversified through selective click chemistry, yielding high-efficiency sulfonate ester products. DFT calculations provide mechanistic insights into the reaction pathway.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Alexander J. Kibler, Nicole Tsang, Max Winslow, Stephen P. Argent, Hon Wai Lam, David Robinson, Graham N. Newton
Summary: Organofunctionalization of polyoxometalates (POMs) allows for the preparation of hybrid molecular systems with tunable electronic properties. This study demonstrates a new functionalization method for Wells-Dawson polyoxotungstate [P2W18O62](6-) using arylarsonic acids, enabling modulation of the redox and photochemical properties. The arylarsonic hybrids show increased visible light photosensitivity and offer a route to stable and tunable organic-inorganic hybrid systems for various redox and photochemical applications.
INORGANIC CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Joshua A. Homer, Long Xu, Namitharan Kayambu, Qinheng Zheng, Eun Joung Choi, Byeong Moon Kim, K. Barry Sharpless, Han Zuilhof, Jiajia Dong, John E. Moses
Summary: SuFEx is a click reaction for rapid synthesis and discovery of functional molecules. This Primer discusses the essential elements of SuFEx operation, catalysis, and SuFExable connective hubs, as well as explores its applications in drug development, polymer science, and biochemistry. It also examines the potential limitations and promising prospects of this versatile click reaction.
NATURE REVIEWS METHODS PRIMERS
(2023)
Article
Chemistry, Physical
Max Winslow, David Robinson
Summary: In this study, derivatives of the widely used 1,6-diphenyl-1,3,5-hexatriene molecular probe were investigated using a multiscale approach. A potential probe for membrane phase and a candidate for an aggregation induced emission fluorophore were identified.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Marie-Claire Giel, Andrew S. Barrow, Christopher J. Smedley, William Lewis, John E. Moses
Summary: This study presents a novel and mild method for catalytic Markovnikov hydration of (E)-aryl enynes to corresponding enones using a bench-stable aminium salt, TBPA. The chemoselective and diastereoselective transformation proceeds under neutral metal-free conditions, delivering excellent product yields. The utility of this transformation is demonstrated through the synthesis of biologically important (E)-3-styrylisocoumarins, including a formal synthesis of achlisocoumarin III.
CHEMICAL COMMUNICATIONS
(2021)
