Article
Chemistry, Organic
Tian Ye, Jinjin Zhao, Wan-Xin Zheng, Junmin Zhang, Zhijuan Wang, Feng-Lian Zhang
Summary: A silyl radical-triggered radical addition-translocation-cyclization (RATC) process has been developed to synthesize structurally diverse silicon-incorporated indolines. The reaction involves silyl radical addition, 1,5-hydrogen atom transfer (HAT), and cyclization, leading to the formation of indoline framework. The substituents attached to the radical center can influence the subsequent reactions, including exclusive hydrogen atom transfer, radical 1,4-silyl migration, and oxidation/deprotonation process. These chemo-divergent reactions provide easy access to silicon-modified indolines from simple starting materials.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Julien Petit, Anthony Cavaille, Nathalie Saffon-Merceron, Marie Fustier-Boutignon, Nicolas Mezailles
Summary: The reduction of a high spin paramagnetic complex by two electrons under N-2 resulted in the formation of two isomeric low spin diamagnetic complexes, which were successfully isolated and characterized. DFT calculations provided insights into the mechanism of double alpha,alpha CH bond insertion into a single sp(3) CH2 moiety. Fast exchange positions of hydrides in the cis dihydride complex were observed using NMR spectrocscopy.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Organic
Hajer Ayachi, Houda Gazzeh, Taoufik Boubaker, Jean-Claude Guillemin
Summary: The key compounds (Z)- and (E)-iminoacetonitriles (NCCH=NH), which are hydrogen cyanide dimers, play important roles in prebiotic chemistry. Methylenecyanamide (CH2=NCN), the second most thermodynamically stable dimer of HCN with covalent bonds, has been poorly studied. We demonstrate that this compound can be isolated, forms stable adducts with nucleophiles or dienes, and can be easily generated under prebiotic conditions, suggesting a potential role in this environment. Comparison between isomers reveals significant differences in formation and chemical reactivity.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Ming-Wei Lin, Hong-Ping Lin, Yi-Wen Ho, Ren-Han Li, Mu-Jeng Cheng, Jong-Liang Lin
Summary: Reflection-absorption infrared spectroscopy, X-ray photoelectron spectroscopy, and temperature-programmed reaction/desorption techniques, together with density-functional-theory calculations, were used to investigate the adsorption and reaction routes of propenoyl chloride on Cu(100) and oxygen-covered Cu(100). The results showed that nucleophilic attack by adsorbed oxygen leads to the formation of propenoate and chlorine on O/Cu(100), while on Cu(100), propenoyl chloride adsorbs and undergoes breakage of the C-Cl bond to form acyl and ketene-like intermediates. The ketene-like intermediate further dimerizes to form a 3-methylene-4-ethenylidene-oxetan-2-one species.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Astronomy & Astrophysics
A. P. Jones
Summary: The aim of the study is to determine the sizes and shapes of nano-diamonds by observing the ratio of their CH2 and CH infrared bands. The results show that the size and shape of nano-diamonds strongly affect this ratio. It is difficult to determine the size of nano-diamonds solely based on the 3-4 μm spectra.
ASTRONOMY & ASTROPHYSICS
(2022)
Article
Engineering, Environmental
Yu Lei, Yafei Yu, Xin Lei, Xi Liang, ShuangShuang Cheng, Gangfeng Ouyang, Xin Yang
Summary: Advanced oxidation processes (AOPs) are widely used for water and wastewater treatment. This study determined second order rate constants for reactions between probes and quenchers with various reactive species and chemical oxidants. Previously ill-quantified reactions were found to be favorable. The improved kinetic database and proposed criteria for probe and quencher selection and dosing will benefit future research in AOPs and other radical-involved reactions.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Meng Wang, Muralidharan Shanmugam, Eric J. L. McInnes, Michael P. Shaver
Summary: Polymeric frustrated radical pairs (poly(FRP)s) were synthesized by in situ photoinduction of FLP moieties, enabling single electron transfer (SET). The radical generation was confirmed by monitoring stable polymeric phosphine radical cations. These new poly(FRP)s exhibited catalytic hydrogenation and radical-mediated photocatalytic perfluoroalkylations, providing new avenues for designing novel functional polymers in catalysis and photoelectrical chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Konstantin W. Kroeckert, Felix Garg, Michel Heinz, Justin Lange, Patricia P. Simoes, Regina Schmidt, Olga Bienemann, Alexander Hoffmann, Sonja Herres-Pawlis
Summary: Copper bromide complexes based on a series of substituted guanidine-quinolinyl and -pyridinyl ligands were investigated, and the relationships between their molecular structures, spectroscopic and electronic properties were described. The study revealed that substituent positions and ligand flexibility have a significant impact on the stability and activity of the copper(ii) complexes.
DALTON TRANSACTIONS
(2022)
Article
Multidisciplinary Sciences
Joshua H. Marks, Jia Wang, Ryan C. Fortenberry, Ralf I. Kaiser
Summary: This article reports the preparation and molecular structure analysis of methanediamine (CH2(NH2)2), the simplest molecule containing the NCN moiety. Methanediamine could be a crucial intermediate in the synthesis of heterocyclic and aromatic systems.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Article
Chemistry, Physical
Gaetan Archer, Kunlong Song, Maurice Medebielle, Jeremy Merad
Summary: The use of free radicals as organocatalysts is a powerful strategy for activating unsaturated carbon chains. Recent advancements in photocatalysis have addressed challenges in catalyst handling and reaction design, allowing for control over the generation and reactivity of radical catalysts. This Concept article highlights the achievements and potential of photocatalyzed covalent radical catalysis.
Review
Chemistry, Multidisciplinary
Israel Fernandez
Summary: This article presents the recent applications of the combination of the Activation Strain Model of reactivity and the Energy Decomposition Analysis methods in understanding the reactivity of Frustrated Lewis Pairs (FLPs). This approach provides deeper insight into the factors controlling cooperative action between Lewis acid/base partners and aids in designing highly active systems for different bond activation reactions.
CHEMICAL COMMUNICATIONS
(2022)
Review
Energy & Fuels
Yann Fenard, Guillaume Vanhove
Summary: Oxymethylene ethers are valuable candidate e-fuels, and research into their combustion properties, particularly focusing on dimethoxymethane, has made significant progress. Future work should focus on precise determination of rate constants for hydrogen atom abstractions and experimental and theoretical studies of longer linear, branched, and cyclic oligomers.
Article
Energy & Fuels
Zhilin Xi, BangXin Jin, Ze Shan
Summary: Research has explored the mechanisms of peroxy radicals in the low temperature oxidation of coal through quantum chemical calculations and analysis of thermodynamic parameters. The study revealed the existence of active sites and different energy barriers and reaction rate constants for chemical adsorption and H transfer reactions involving ROO.. Additionally, an antioxidant enzyme inhibitor compound containing superoxide dismutase (SOD) was found to effectively eliminate ROO., providing theoretical support for coal spontaneous combustion prediction.
Article
Thermodynamics
Caiyu Yang, Jin-Tao Chen, Xincheng Zhu, Xin Bai, Yang Li, Kiran K. Yalamanchi, S. Mani Sarathy, S. Scott Goldsborough, Song Cheng, Henry J. Curran, Chong-Wen Zhou
Summary: This study systematically investigates the hydrogen atom abstraction by methyl peroxy (CH3OO) radicals in the gasoline/ethanol interacting chemistry. The high-pressure limiting rate constants for various components were calculated, and it was found that the abstraction of allylic hydrogen atoms from 1-hexene is the fastest at low temperatures.
PROCEEDINGS OF THE COMBUSTION INSTITUTE
(2023)
Article
Chemistry, Physical
Jorge Alonso de la Fuente, Cristina Sanz-Sanz, Lola Gonzalez-Sanchez, Ersin Yurtsever, Roland Wester, Francesco A. Gianturco
Summary: We conducted accurate ab initio calculations on a gas-phase system in the interstellar medium (ISM) which has been speculated but not yet observed. The study focuses on the collision dynamics between the molecular anion and He atoms and evaluates their potential energy surface (PES). Inelastic scattering cross sections and rate coefficients are computed, suggesting that collision-induced changes in the rotational state populations of this anion are inefficient, which may affect its observation through direct radiative emission in the microwave region.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Baptiste Picard, Katia Perez, Thomas Lebleu, Daniela Vuluga, Fabrice Burel, David C. Harrowven, Isabelle Chataigner, Jacques Maddaluno, Julien Legros
JOURNAL OF FLOW CHEMISTRY
(2020)
Article
Chemistry, Organic
Faisal A. Almalki, Wei Sun, Mark E. Light, David C. Harrowven
Article
Chemistry, Multidisciplinary
Wei Sun, William A. T. Raimbach, Luke D. Elliott, Kevin I. Booker-Milburn, David C. Harrowven
Summary: An oxidative photocyclisation of N-arylenaminones to indoles is presented, using anilines instead of arylhydrazines in a process reminiscent of the Fischer indole synthesis. This method demonstrates new approaches to synthesizing WHO-listed APIs such as ondansetron and alosetron.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Wei Sun, Surajit Kayal, William A. T. Raimbach, Xue-Zhong Sun, Mark E. Light, Magnus W. D. Hanson-Heine, Michael W. George, David C. Harrowven
Summary: The passage discusses the synthesis of compounds using ninhydrin bis-acetals through photoextrusion and tandem photoextrusion reactions. The value of the method is demonstrated by the synthesis of various compounds, and mechanistic insights into their wavelength dependence are provided through TA spectroscopy and TD-DFT studies.
CHEMICAL COMMUNICATIONS
(2022)
Article
Materials Science, Multidisciplinary
Sasikumar Arumugam, Yi Li, James E. Pearce, Katie L. Court, Giacomo Piana, Edward H. Jackman, Oliver J. Ward, Martin D. B. Charlton, John Tudor, David C. Harrowven, Steve P. Beeby
Summary: In this study, a series of printable UV emitting ionic bifluorene derivatives were successfully synthesized and demonstrated electroluminescence in the UV range through ink formulation and spray coating methods.
ORGANIC ELECTRONICS
(2022)
Article
Chemistry, Multidisciplinary
Ana A. Folgueiras-Amador, Alexander E. Teuten, Mateo Salam-Perez, James E. Pearce, Guy Denuault, Derek Pletcher, Philip J. Parsons, David C. Harrowven, Richard C. D. Brown
Summary: The electro-reductive radical cyclisation of aryl halides using an organic mediator in an undivided flow reactor is a practical and efficient method to synthesize hetero- and carbo-cycles. The use of a sub-stoichiometric amount of mediator increases its practical utility. This methodology is versatile and can be applied to different tethering groups, resulting in the formation of diverse cyclic compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Darren S. Lee, Ashley Love, Zakaria Mansouri, Toby H. Waldron Clarke, David C. Harrowven, Richard Jefferson-Loveday, Stephen J. Pickering, Martyn Poliakoff, Michael W. George
Summary: The development of a single-pass electrochemical Birch reduction in a small footprint electrochemical reactor is reported, achieving high selectivity and productivity by varying the current and solution composition.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2022)
Article
Chemistry, Multidisciplinary
Robert C. Carroll, David C. Harrowven, James E. Pearce, Simon J. Coles
Summary: The utilization of the crystalline sponge method enables the characterization of a novel family of synthetic organic oils. The structural differences and functional group diversity provided by 13 related molecular adsorbates offer a quantitative understanding of the relationship between guest structure, conformation, and intermolecular interactions with neighboring guests and the host framework. This analysis extends to assess the connection between these factors and the quality indicators for molecular structure elucidation.
Article
Chemistry, Multidisciplinary
Matthieu Hedouin, Eleonora Luppi, Oliver Ward, David Harrowven, Catherine Fressigne, Isabelle Chataigner
Summary: In this study, the absorption and emission properties of a series of 44 aromatic molecules were investigated using different exchange-correlation functionals in Time Dependent Density Functional Theory (TDDFT). Solvent effects were included using linear response (LR) and state specific (SS) polarisable continuum model (PCM). The comparison with experimental UV-Vis data showed reasonable agreement when using & omega;B97XD with SS-PCM. An accurate linear correlation between experimental and theoretical results was found, leading to equations for absorption and emission derived from a linear fitting between theoretical and experimental data. Through these linear equations, a simple, pragmatic, and cost-effective approach for describing and predicting the absorption and emission of aromatic molecules was proposed.
Article
Chemistry, Multidisciplinary
Wei Sun, Luke Wilding-Steele, Richard C. D. Brown, David C. C. Harrowven
Summary: Benzyloxy iodobenzene ethers can undergo cyclisation to form benzo[c]chromenes under UVC irradiation without the need for reagents or catalysts. The reactions proceed through the generation of triplet aryl cations, 5-exo and 3-exo-cyclisations, and subsequent rearomatisation. This methodology is versatile, convenient, and applicable to various related ring systems.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Jack W. Hodgson, Ana A. Folgueiras-Amador, Derek Pletcher, David C. Harrowven, Guy Denuault, Richard C. D. Brown
Summary: In electrosynthesis, the choice of electron transfer (ET) mediators plays a crucial role in achieving selective heterogeneous electron transfer. This study explores a counterintuitive situation where the mediator has a lower reduction potential than the substrate, leading to a detached reaction layer and a different reaction pathway. Simulations and experiments on electroreductive cyclisation support the potential use of highly reducing homogeneous ET agents in mediated electrosynthesis.
FARADAY DISCUSSIONS
(2023)
Article
Chemistry, Multidisciplinary
Batoul Rkein, Romain Coffinier, Marian Powderly, Maxime Manneveau, Morgane Sanselme, Muriel Durandetti, Muriel Sebban, Ghanem Hamdoun, Hassan Oulyadi, David Harrowven, Julien Legros, Isabelle Chataigner
Summary: This article investigates the reaction of nitroarenes with silyloxydienes under high pressure and demonstrates the successful dearomatizing [4+2] cycloadditions at room temperature, resulting in highly functionalized compounds with tetrasubstituted carbon centers.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Morgan A. Manning, Wei Sun, Mark E. Light, David C. Harrowven
Summary: A new route to azocines and benzoazocines from furopyridinones is described through a photochemically induced [1,3]-sigmatropic rearrangement. The method provides excellent atom economy by sequencing thermal and photochemical ring expansion steps under continuous flow.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Ryan M. Bennett, Wei Sun, Dharyl C. Wilson, Mark E. Light, David C. Harrowven
Summary: This research discusses a dichotomy in the additions of organolithiums and lithium amides to cyclobutenediones, resulting in different products. The distinct mode of ring scission allows for the synthesis of 2-oxobut-3-enamides and tetrasubstituted furans.
CHEMICAL COMMUNICATIONS
(2021)
Proceedings Paper
Engineering, Manufacturing
Sasikumar Arumugam, Yi Li, Katie Court, Giacomo Piana, Martin Charlton, John Tudor, David Harrowven, Steve Beeby
Summary: The development of light emitting textiles using OLECs and conductive organic materials has shown promising results in terms of brightness, color emission, and operational stability. The solution processed fabrication method on ITO coated glass substrates with commercially available blue emitter has enabled the operation of blue emitting LECs in ambient environment for the first time. Encapsulation process is utilized to protect the glass based OLECs from oxygen and moisture, enhancing device performance stability and lifetime.
PROCEEDINGS OF THE 2021 IEEE INTERNATIONAL CONFERENCE ON FLEXIBLE AND PRINTABLE SENSORS AND SYSTEMS (FLEPS)
(2021)
Article
Chemistry, Organic
Faiza Diaba, Gisela Trenchs
Summary: The first violet light-mediated synthesis of gamma- and delta-lactams from N-alkenyl trichloroacetamides is reported in this paper. The reactions are conducted in tetrahydrofuran or 2-methyltetrahydrofuran as the sole solvent without catalysts or additives, under non-anhydrous conditions in an air atmosphere where the solvent serves as the radical initiator.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Feroze Hussain, Sajjad Ahmed, Ashiq Hussain Padder, Qazi Naveed Ahmed
Summary: This study reports a novel and efficient one-pot synthesis method for mixed phosphorotrithioates, which does not require supplementary additives and shows broad applicability.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Hyunjin Oh, Ikyon Kim
Summary: A new 1,2,4-triazole-pyrrolo[1,2-a]pyrazine hybrid system, 6-acylpyrrolo[1,2-a][1,2,4]triazolo[5,1-c]pyrazine, was synthesized using a catalyst-free method. This method involved sequential exposure of pyrrole-2-carbonitrile-derived substrates to DMF-DMA and acyl hydrazide, resulting in the formation of acylated pyrazine and 1,2,4-triazole rings, enabling the installation of various substituents at specific positions on the core skeleton.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Ming Yan, Si-fan Wang, Yong-po Zhang, Jin-zhong Zhao, Zhuo Tang, Guang-xun Li
Summary: Here we developed an efficient photocatalytic approach for the convenient preparation of sulfinamides. The reaction allows for the gram-scale preparation of sulfinamides and the one-pot synthesis of various sulfonyl amides.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Farzaneh Bandehali-Naeini, Zahra Tanbakouchian, Noushin Farajinia-Lehi, Nicolas Mayer, Morteza Shiri, Martin Breugst
Summary: Two tandem catalytic systems were developed for the synthesis of novel 3,4-disubstituted maleimides using the same Ugi adducts. Different maleimide structures can be synthesized using either Pd or Cu catalysis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Tanya Raghava, Anjan Chattopadhyay, Subhadeep Banerjee, Nivedita Sarkar
Summary: Amine substitution of two ortho fluorine atoms of tetrafluoroterephthalonitrile through SNAr chemistry is easily achievable. But further fluorine substitution is only possible under forcing conditions, yielding valuable fluorophores for bioimaging.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Review
Chemistry, Organic
Anju Chadha, Santosh Kumar Padhi, Selvaraj Stella, Sowmyalakshmi Venkataraman, Thangavelu Saravanan
Summary: Alcohol dehydrogenases are enzymes that use cofactors for oxidation or reduction reactions of alcohols or carbonyl compounds. They are utilized in green chemistry and have applications in the production of pharmaceuticals. Recombinant enzymes have solved the challenge of producing purified enzymes in large quantities. Engineered alcohol dehydrogenases have been used in asymmetric synthesis in industry. Various methods have been established for regenerating expensive cofactors to make the enzymatic process more efficient and economically viable.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
