Article
Chemistry, Multidisciplinary
Jingyang Qin, Manuel Barday, Samikshan Jana, Nil Sanosa, Ignacio Funes-Ardoiz, Christopher J. Teskey
Summary: A mild and selective hydropyridylation method for dienes was reported, allowing for traceless coupling of dienes on a wide range of pyridine substrates. The method showed good functional group tolerance, making it suitable for late-stage functionalization. The mechanistic pathway involved non-reversible hydrogen atom transfer, resulting in a reaction that was uniquely selective for dienes in the presence of other olefins.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Jonas Elfert, Anup Bhunia, Constantin G. Daniliuc, Armido Studer
Summary: In this study, a radical transformation that enables intramolecular oxygen atom transfer to alkenes using the nitro functionality in nitroarenes as an oxygen donor is disclosed. The reaction proceeds via iron-catalyzed metal hydrogen atom transfer to alkenes and subsequent oxygenation, resulting in alkene hydration. Compared to intermolecular radical oxygenation, the intramolecular variant offers advantages, particularly in terms of diastereoselective radical hydration of conformationally flexible alkenes. The aryl moiety connecting the reactive NO2-functionality to the alkene substrate can be cleaved after oxygen transfer, yielding products derived from a formal diastereoselective intermolecular alkene hydration. Additionally, the resulting aniline entity after oxygen transfer can be used for the construction of nitrogen-containing heterocycles.
Article
Chemistry, Applied
Nicholas D. C. Tappin, Philippe Renaud
Summary: An improved procedure for halogen atom and chalcogen group transfer radical additions is reported, utilizing the thermal decomposition of DTBHN to produce reactive methyl radicals. This initiation method generates gaseous or volatile byproducts for easy purification, with simple reaction conditions and broad scope of application demonstrated. Additionally, an alternative source of radicals, DTBPO, is also shown to be effective under identical conditions.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Robert D. Riley, Blake S. N. Huchenski, Karlee L. Bamford, Alexander W. H. Speed
Summary: This study demonstrates that diazaphospholene hydrides can be regenerated by the combination of phenylsilane and alkali metal salts, enabling catalytic radical reactions of aryl iodides. The method is not only applicable to aryl iodides, but can also be extended to aryl bromides, which benefit from visible light irradiation. Additionally, intermolecular radical hydroarylation reactions with arenes, thiophenes, and a pyridine have been successfully achieved.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Physical
Moises A. de Araujo, Andrey A. A. Koverga, Alan M. P. Sakita, Felipe B. B. Ometto, Leticia G. da Trindade, Edson A. A. Ticianelli
Summary: The review provides a comprehensive account of recently reported strategies to enhance the electrocatalytic reduction of O-2, CO2, and water on M-N-C catalysts, as well as discusses the latest theoretical studies based on computer modelling and simulation. It aims to offer an in-depth understanding of these reactions and provide future perspectives for guiding new research.
Article
Green & Sustainable Science & Technology
Sajjad Hussain, Dhanasekaran Vikraman, Zeesham Abbas, Muhammad Faizan, Sikandar Aftab, Khalid Mujasam Batoo, Hyun-Seok Kim, Kyung-Wan Nam, Jongwan Jung
Summary: In this study, CoNiO2 nanowires (NWs)-embedded MoS2 hybrids were synthesized and found to exhibit superior bifunctional catalytic activity and stability. The strong interfacial contact between CoNiO2 NWs and MoS2 was also observed, contributing to the enhanced electrocatalytic performance. This development of cobalt-based oxide and transition metal dichalcogenide carrier bifunctional electrocatalysts provides a novel approach to enhance overall water splitting.
SUSTAINABLE MATERIALS AND TECHNOLOGIES
(2023)
Article
Chemistry, Multidisciplinary
Sripati Jana, Chao Pei, Claire Empel, Rene M. Koenigs
Summary: Controlling the reactivity of diaryl carbenes can be achieved by manipulating the electronic properties of the substituents, allowing for highly chemoselective carbene transfer reactions without the need for external additives. Photolysis of diazo compounds can readily access the free diaryl carbenes, which can then undergo various chemoselective reactions. Experimental and theoretical analyses confirm the involvement of different carbene spin states in rationalizing the observed reactivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Physical
Lord Ikechukwu Ugwu, Yasser Morgan, Hussameldin Ibrahim
Summary: Hydrogen can be generated from various feedstocks by using heterogeneous catalysts to speed up reactions. Combining experimental and computational studies can provide a comprehensive understanding of the reactions, and the combination of machine learning and density functional theory holds great potential.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2022)
Article
Chemistry, Multidisciplinary
Abhishek Koner, Bernd Morgenstern, Diego M. Andrada
Summary: A new N-heterocyclic carbene-stabilized phosphaborene has been synthesized and isolated, which is a room-temperature-stable crystalline solid. It exhibits remarkable reactivity and can undergo P-centre metathesis reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Kosuke Nakashima, Anton Petek, Yutaro Hori, Anton Georgiev, Shin-ichi Hirashima, Yasuyuki Matsushima, Dancho Yordanov, Tsuyoshi Miura, Liudmil Antonov
Summary: This study demonstrates the reimagined concept of long-range tautomeric proton transfer using crane subunits by designing and synthesizing two new acylhydrazones. The acylhydrazone subunits attached to the 7-OHQ act as crane arms for delivering protons to the quinoline nitrogen, providing different proton transport pathways with steric strain from the -CH3 group. Both compounds exhibit long thermal stability in the switched state, enabling tunable bidirectional proton cargo transport using different wavelengths of irradiation.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Review
Biochemistry & Molecular Biology
Fang Li, Jingqin Xu, Yajie Wang, Haiyan Zheng, Kuo Li
Summary: Under pressure, unsaturated organic molecules tend to form covalent bonds to polymerize and create polymeric materials with extended carbon skeleton. The polymerization reactions typically occur in crystals, promoting the topochemical process.
Article
Chemistry, Multidisciplinary
Xinyao Li, Johannes Grosskopf, Christian Jandl, Thorsten Bach
Summary: 3-Substituted quinoxalin-2(1H)-ones and various aryl-substituted or tethered olefins can undergo an enantioselective aza Paterno-Buchi reaction upon irradiation with a chiral sensitizer at lambda=420 nm. The absolute and relative configuration of the products were elucidated by X-ray crystallography, suggesting triplet energy transfer in a hydrogen-bonded complex between the imine substrate and the catalyst. Preliminary experiments also explored intramolecular cycloaddition and alternative reaction modes of quinoxalinones.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Organic
Sandeepan Maity
Summary: Samarium diiodide (SmI2) is a versatile single electron transfer reagent used in organic synthesis for stereoselective reactions. However, its stoichiometric usage poses environmental concerns limiting its broader applicability. Recent studies have focused on developing catalytic methods to rejuvenate the applications of SmI2 in synthetic organic chemistry.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Dongsheng Zhang, Ren Su
Summary: Heterogeneous photocatalysis is a promising method for hydrogenative reactions due to its mild reaction conditions and the use of liquid hydrogen donors. The current focus is on developing high-performance photocatalyst materials and expanding the range of reactions. However, there is a lack of overview on the mechanistic understanding of light-induced hydrogenative reactions from the perspective of hydrogen donors. In this study, we categorized photocatalytic hydrogenative reactions based on the type of liquid hydrogen donors (hydrocarbons and water), discussed the criteria for hydrogen abstraction from these donors, and elaborated on the design strategy of photocatalyst materials.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Nikoleta Spiliopoulou, Petros L. Gkizis, Ierasia Triandafillidi, Nikolaos F. Nikitas, Charikleia S. Batsika, Aikaterini Bisticha, Christoforos G. Kokotos
Summary: In this paper, we restudied the mechanism of action of phenylglyoxylic acid (PhCOCOOH) in photochemical reactions and proposed a unified mechanism. Additionally, we compared its action as a photoinitiator with known and commercially available photoinitiators.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Yuki Hyodo, Keigo Takahashi, Youhei Chitose, Manabu Abe, Michito Yoshizawa, Takashi Koike, Munetaka Akita
Summary: The host-guest assemblies of a designed compound and V-shaped aromatic amphiphiles proved to be effective photoredox catalysis systems with high reducing activity in water, particularly for the demethoxylative hydrogen transfer of Weinreb amides. This supramolecular strategy allows for easy tuning of visible-light photoredox catalysis in water.
Article
Biochemistry & Molecular Biology
Michael Wenk, Jean-Marc Nuzillard, Christoph Steinbeck
Summary: The publication introduces Sherlock, a free and open-source Computer-Assisted Structure Elucidation (CASE) software that allows the structure elucidation of small organic molecules (<1500 Dalton) through 1D and 2D NMR data analysis. Sherlock offers a versatile graphical user interface for spectral peak picking, addition of structure constraints, structure generation, ranking, and display of solutions, thus improving the reliability and traceability of structure elucidation results for organic chemists.
Review
Chemistry, Multidisciplinary
Arthur Desvals, Norbert Hoffmann
Summary: Photocycloadditions of benzene derivatives with alkenes are important in organic synthesis, especially intramolecular reactions. Competition between meta or [2 + 3] photocycloadditions and ortho or [2 + 2] additions is common. The influence of substitution pattern and spin multiplicity on reaction outcomes is discussed. A topological analysis allows for systematic application of [2 + 3] photocycloadditions in total synthesis of natural products, with corresponding syntheses discussed. Recent research has also focused on [2 + 2] photocycloadditions and consecutive rearrangements in organic synthesis, including approaches in asymmetric synthesis.
AUSTRALIAN JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yuki Miyazawa, Zhe Wang, Sayaka Hatano, Ryukichi Takagi, Hideto Matsuoka, Naoka Amamizu, Yasutaka Kitagawa, Eiichi Kayahara, Shigeru Yamago, Manabu Abe
Summary: This study characterized the magnetic interactions in a tetraradical embedded in a curved benzene structure and found unique spin-spin interactions, ring-size effects, and in-plane aromaticity. Triplet species with similar properties as a diphenylcyclopentane diradical were observed, but the quintet state resulting from ferromagnetic interaction was not detected. The singlet state was found to be lower in energy than the triplet and quintet states at a theoretical level. These findings are important for the development of open-shell species in material science.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Sobiya George, Dmitrii Govorov, DeVonna M. Gatlin, Rajkumar Merugu, Fiona J. Wasson, Dylan J. Shields, Yasmine Allen, Sivaramakrishnan Muthukrishnan, Jeanette A. Krause, Manabu Abe, Anna D. Gudmundsdottir
Summary: Irradiation of p-methoxyazidobutyrophenone (1) in methanol led to the formation of 2-(4-methoxyphenyl)-1-pyrroline (2) and several other photoproducts. In the presence of tris-(trimethylsilyl)-silane (TTMSS), 2 was selectively formed. Transient absorption and ESR spectroscopy confirmed the formation of triplet alkylnitrene (3) 1N through intramolecular energy transfer from the triplet ketone (T-1K). DFT calculations revealed that (3) 1N abstracts H atoms from TTMSS but not methanol, explaining the observed selectivity. Therefore, triplet alkylnitrenes can undergo selective reductive cyclization via H atom abstraction from TTMSS.
Article
Multidisciplinary Sciences
Eiji Shirakawa, Yuki Ota, Kyohei Yonekura, Keisho Okura, Sahiro Mizusawa, Sujan Kumar Sarkar, Manabu Abe
Summary: An electron has been found to catalyze the cross-coupling reaction of organometallic compounds with aryl halides, which is more desirable for green and sustainable chemistry compared to transition metal catalysis. However, high temperature is required for this electron catalysis. We discovered that visible light photoirradiation can accelerate the electron-catalyzed reaction by using photoredox catalysis, enabling the reaction to proceed at room temperature. The supply of the electron catalyst through photoredox catalysis also expands the scope of aryl halides.
Article
Chemistry, Organic
Masato Kondoh, Shunsuke Kuboki, Hidetaka Kume, Eriku Oda, Manabu Abe, Taka-aki Ishibashi
Summary: This study investigates the bonding properties of singlet and triplet cyclopentane-1,3-diyl diradicals (DRs) with C=O and C equivalent to N groups. The effects of unpaired electrons on the bond properties of C=O and C equivalent to N in DRs strongly depend on its spin multiplicity. These findings provide valuable insights for research in both organic and theoretical chemistry.
JOURNAL OF PHYSICAL ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jean-Marc Nuzillard
Summary: The quick identification of known organic low molecular weight compounds, also known as structural dereplication, is a highly important task in the chemical profiling of natural resource extracts. This article presents the results of structure searches carried out starting from 58 carbon-13 NMR data sets recorded on compounds selected in the metabolomics section of the biological magnetic resonance bank (BMRB). Two compound retrieval methods were employed, and both methods proved to be efficient and can be used together in a complementary way.
MAGNETIC RESONANCE IN CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Julien Cordonnier, Simon Remy, Jean-Hugues Renault, Jean-Marc Nuzillard
Summary: Compound identification in complex mixtures by NMR and MS is best achieved through experimental databases mining. However, these databases often have limitations, leading to the use of predicted databases. This study focuses on filtering a large database before searching for unlikely structure candidates.
Article
Chemistry, Analytical
Francois Pedinielli, Ritchy Leroy, Salah-Eddine Akrial, Anthony Robert, Jean-Marc Nuzillard, Pedro Lameiras
Summary: ViscY offers a new method to analyze time-varying complex mixtures, and this study demonstrates its use in monitoring chemical reactions and characterizing a 3-substituted 4-hydroxycoumarin derivative and its side-product in real-time using the viscous binary solvent DMSO-d(6)/water.
Article
Chemistry, Organic
Mohammed Latrache, Corentin Lefebvre, Manabu Abe, Norbert Hoffmann
Summary: Photochemically induced intramolecular hydrogen atom transfer in oxazolones has been reported. The reaction produces C-C or C-N bond formation. The regioselectivity of the reaction is determined by the zwitterionic structure in the singlet state.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Stefan Kuhn, Jean-Marc Nuzillard
Summary: This article introduces the creation and usage of a general natural product database for the dereplication of natural products. The database, called acd_lotusv7, is built upon the LOTUS natural products database and uses ACD/C+H Predictors and DB software for predicting carbon-13 nuclear magnetic resonance (NMR) spectral data. The database is linked to Wikidata resources for accessing primary literature data. The open source nmrshiftdb2 web interface and search engine allow easy and free retrieval of compound structures from carbon-13 data. Three natural compounds of different complexities were successfully dereplicated using published carbon-13 NMR chemical shifts.
Article
Chemistry, Analytical
Ritchy Leroy, Francois Pedinielli, Gautier Bourbon, Jean-Marc Nurzillard, Pedro Lameiras
Summary: This study presents the use of diethanolamine/DMSO-d6 as a binary solvent for the individualization of low-polarity mixture components. The viscosity of the solvent induces molecular tumbling, which promotes magnetization transfer and allows for mixture analysis. Various experiments, including NOESY and HSQC-NOESY experiments, were performed to separate four low-polarity chemical compounds dissolved in the solvent blend.
ANALYTICAL CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Hiroto Yoshida, Yuki Izumi, Yuta Hiraoka, Kazuki Nakanishi, Masaaki Nakamoto, Sayaka Hatano, Manabu Abe
Summary: This article describes the synthesis of a new stable compound PhMe2Si-B(dan) and its application in catalytic silylboration and silylation reactions of alkynes.
DALTON TRANSACTIONS
(2022)
