Article
Chemistry, Multidisciplinary
Anthony F. Tierno, Jennifer C. Walters, Andres Vazquez-Lopez, Xiao Xiao, Sarah E. Wengryniuk
Summary: This study utilizes N-HVI reagents as heterocyclic group transfer reagents to provide a broad scope of N-alkyl(heteroaryl)onium salts via aminolactonization of alkenoic acids, showcasing a novel method for their synthesis.
Article
Multidisciplinary Sciences
Owen Smith, Mihai V. Popescu, Madeleine J. Hindson, Robert S. Paton, Jonathan W. Burton, Martin D. Smith
Summary: This paper reports the design, synthesis and characterization of a helically chiral triaryloxonium ion that functions as a determinant of configuration. It is the only example of a chiral non-racemic and configurationally stable molecule in which the oxygen atom is the sole stereogenic centre.
Article
Chemistry, Organic
Jun-Qi Zhang, Jiayue Liu, Dandan Hu, Jinyu Song, Guorong Zhu, Hongjun Ren
Summary: This study proposes a green alternative method using aqueous ammonia as the N source for the cyanating reagent, entirely avoiding the use of toxic cyanating reagents or metal catalysis.
Article
Chemistry, Organic
Jun-Qi Zhang, Jiayue Liu, Dandan Hu, Jinyu Song, Guorong Zhu, Hongjun Ren
Summary: A scalable cyanation method for the synthesis of (hetero)arylacetonitrile derivatives from gem-difluoroalkenes has been developed. This method offers mild reaction conditions, excellent yields, a wide range of applicable substrates, and tolerance to various functional groups. Notably, the use of aqueous ammonia as a nitrogen source eliminates the need for toxic cyanating reagents or metal catalysts, providing a green and alternative approach for the synthesis of arylacetonitriles.
Article
Multidisciplinary Sciences
Jae Bin Lee, Gun Ha Kim, Ji Hwan Jeon, Seo Yeong Jeong, Soochan Lee, Jaehyun Park, Doyoung Lee, Youngkook Kwon, Jeong Kon Seo, Joong-Hyun Chun, Seok Ju Kang, Wonyoung Choe, Jan-Uwe Rohde, Sung You Hong
Summary: The authors present a transition-metal-free, radical relay pi-extension approach to produce N-doped polycyclic aromatic compounds directly from simple azines and cyclic iodonium salts. This method offers a solution to the limitation of low reactivity in unactivated azines.
NATURE COMMUNICATIONS
(2022)
Review
Chemistry, Organic
Eiji Tayama
Summary: The Sommelet-Hauser rearrangement of X-benzylic onium ylides is an important transformation in organic synthesis. Recent studies in the past 15 years have greatly expanded the scope and synthetic applications of this reaction.
SYNTHESIS-STUTTGART
(2022)
Article
Polymer Science
Paulina Bednarczyk, Alicja Balcerak-Wozniak, Janina Kabatc-Borcz, Zbigniew Czech
Summary: This study investigates novel two-component photoinitiating systems for the radical polymerization of (meth)acrylate-based compositions. The proposed systems consist of a squaraine dye as a photosensitizer and various onium salts as co-initiators. The newly synthesized squaraines, SQN1 and SQN2, were used in combination with commercially available co-initiators I1 and NO, as well as the newly synthesized NO1. The new photoinitiators demonstrate high activity for the polymerization of (meth)acrylates activated by UV-Vis light. The squaraine derivatives effectively initiate the radical polymerization of methacrylate and acrylate monomers, with conversion rates ranging from 40% to 100% for methacrylates and 30% to 100% for acrylates.
Article
Chemistry, Multidisciplinary
Dmitry Pasyukov, Maxim A. Shevchenko, Konstantin E. Shepelenko, Oleg Khazipov, Julia Burykina, Evgeniy G. Gordeev, Mikhail E. Minyaev, Victor M. Chernyshev, Valentine P. Ananikov
Summary: In this study, a new strategy for the synthesis of imidazolium and imidazolinium salts from easily available compounds was reported. The researchers discovered a family of unprecedented reactions that can achieve nucleophilic addition and cyclization in one step. The synthesized N-heterocyclic carbene precursors can be directly metallated to produce functionalized metal/carbene complexes. The obtained compounds showed good activity in catalytic model reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Chun-Xiang Guo, Sivathmeehan Yogendra, Rosa M. Gomila, Antonio Frontera, Felix Hennersdorf, Johannes Steup, Kai Schwedtmann, Jan J. Weigand
Summary: The study successfully synthesized a family of electrophilic fluorophosphonium cations as triflate salts by in situ electrophilic fluorination of phosphanes, followed by subsequent methylation of the anion. These fluorophosphonium triflate salts exhibit remarkable Lewis acidity and form isolable adducts in stoichiometric reactions with suitable donors. Additionally, their catalytic capabilities were tested in a specific transformation reaction and validated by DFT calculations.
INORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Aleksandra Nilova, Bryan Metze, David R. Stuart
Summary: Controlling reaction pathways selectively leads to a broad scope of arenes and arynophiles, offering efficient access to diverse arene chemical space and biologically active compounds with high yields.
Article
Chemistry, Multidisciplinary
Thomas Delouche, Elsa Caytan, Marie Cordier, Thierry Roisnel, Gregory Taupier, Yann Molard, Nicolas Vanthuyne, Boris Le Guennic, Muriel Hissler, Denis Jacquemin, Pierre-Antoine Bouit
Summary: We report a straightforward synthesis method for novel P-heterocycles. These compounds exhibit good stability and can be post-functionalized with different substituents. They are also suitable for the preparation of more complex polyaromatic scaffolds. Our study shows that molecular engineering can not only tune the optical properties of these compounds but also impart them with special optical properties.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Marcel Buerger, Nadine Ehrhardt, Thomas Barber, Liam T. Ball, Jan C. Namyslo, Peter G. Jones, Daniel B. Werz
Summary: A phosphine-catalyzed oligomerization of arynes using selenocyanates has been developed to access alpha, omega-bisfunctionalized oligo(ortho-arylenes). The use of JohnPhos as a bulky phosphine catalyst is crucial for this reaction to occur. Various optimized conditions have been established to predominantly form dimers, but also higher oligomers, up to octamers, depending on the electronic properties of the electrophilic reaction partner. Mechanistic studies show that the cascade reaction starts with cyanide attack and rules out aryne insertion into n-mers leading to (n+1)-mers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Hui Wu, Youqing He, Kai Sun, Yaling Xu, Wenting Wang, Ge Wu
Summary: A method for iodine(iii)-mediated dehydroaromatization of cyclohexanones with primary amines and CD3SSO3Na has been developed, providing direct access to ortho-SCD3 anilines with the formation of C-N and C-S bonds. Detailed mechanism studies indicate that hypervalent iodine(iii) plays dual roles as an efficient mediator and an oxidant, and the continuously generated alpha-acetoxylated ketones and alpha-SCD3 ketones are the key intermediates in the current three-component reactions. The present transformations demonstrate excellent chemo-selectivity and are applicable for late-stage modification of numerous pharmaceuticals.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Multidisciplinary Sciences
Jan Vrana, Josef Holub, Maksim A. Samsonov, Zdenka Ruzickova, Josef Cvacka, Michael L. McKee, Jindrich Fanfrlik, Drahomir Hnyk, Ales Ruzicka
Summary: In contrast to the prevalence of neutral or anionic species, the authors have developed a method to prepare water-soluble cationic polyhedral boranes by reacting closo-10-vertex carboranes with N-heterocyclic carbenes. These cationic boron clusters may have potential for novel applications.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Gurupada Hazra, Ahmad Masarwa
Summary: Here, we present a simple and efficient method for obtaining a diverse range of thiophosphonium salts. This method involves the direct coupling of commercially available thiols and aldehydes with Ph3P and TfOH, without the need for metal catalysts. The synthesized salts demonstrate high synthetic utility through various examples of C-P bond functionalizations, enabling the synthesis of valuable building blocks in high yields.
Article
Chemistry, Multidisciplinary
Clement Ghiazza, Vincent Debrauwer, Cyrille Monnereau, Lhoussain Khrouz, Maurice Medebielle, Thierry Billard, Anis Tlili
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2018)
Article
Chemistry, Organic
Clement Ghiazza, Cyrille Monnereau, Lhoussain Khrouz, Maurice Medebielle, Thierry Billard, Anis Tlili
Article
Chemistry, Organic
Clement Ghiazza, Alex Kataria, Anis Tlili, Fabien Toulgoat, Thierry Billard
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2019)
Article
Chemistry, Multidisciplinary
Jeroen B. Sap, Natan J. W. Straathof, Thomas Knauber, Claudio F. Meyer, Maurice Medebielle, Laura Buglioni, Christophe Genicot, Andres A. Trabanco, Timothy Noel, Christopher W. am Ende, Veronique Gouverneur
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Chemistry, Multidisciplinary
Thomas Criton, Debora Vilona, Guy Jacob, Maurice Medebielle, Elise Dumont, Lionel Joucla, Emmanuel Lacote
Summary: Polyazanes, higher nuclearity homologues of hydrazines with increasing numbers of bound nitrogen atoms (from 3 to 5), including the first pentazane ever described, were prepared by adding lower-order polyazanes to diazo reagents. A helical conformation of the polynitrogen chains was observed, which persists in solution based on DFT modeling. Despite being reducing agents, polyazanes become less reducing as the number of nitrogens increases.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Clemence Bonnefoy, Emmanuel Chefdeville, Armen Panosian, Gilles Hanquet, Frederic R. Leroux, Fabien Toulgoat, Thierry Billard
Summary: Despite recent advances, trifluoromethoxylation is still a challenging reaction. This study presents an efficient trifluoromethoxylative substitution using an inexpensive and easy-to-handle reagent, which involves mixing DMAP with a slight excess of 1,4-dinitro-trifluoromethoxybenzene to obtain a stable solution of trifluoromethoxide anion for S(N)2 reaction without any silver additives. Detailed investigation on the properties and behavior of this stable CF3O- species is conducted.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Anais Loison, Fabien Toulgoat, Thierry Billard, Gilles Hanquet, Armen Panossian, Frederic R. Leroux
Summary: The fluorine atom and fluorinated substituents play important roles in pharmaceutical and agrochemical active ingredients, beneficially modulating their properties. Among these, the -OCHF2 group is emerging as an interesting motif capable of forming hydrogen bonds. There is a growing need for methods to introduce this group.
Article
Chemistry, Multidisciplinary
Alexis Taponard, Tristan Jarrosson, Lhoussain Khrouz, Maurice Medebielle, Julie Broggi, Anis Tlili
Summary: The activation of SF6 under metal-free and visible light conditions was investigated and a new fluorinating reagent was synthesized. This reagent was efficient in the deoxyfluorination of CO2 and fluorinative desulfurization of CS2 to produce useful fluorinated amines. Additionally, the reagent was able to generate Cl-SF5 gas, which was used for the chloro-pentafluorosulfanylation of alkynes and alkenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Clemence Bonnefoy, Emmanuel Chefdeville, Christian Tourvieille, Armen Panossian, Gilles Hanquet, Frederic Leroux, Fabien Toulgoat, Thierry Billard
Summary: This paper presents a study on the properties and potential applications of carbamoyl fluoride, including stability, lipophilicity, and synthesis methods. The results demonstrate its potential use in radiochemistry.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Kevin Grollier, Clement Ghiazza, Anis Tlili, Thierry Billard, Maurice Medebielle, Julien C. Vantourout
Summary: A practical electrochemical method is reported in this study for the generation of CF3Se- anion from a stable reagent (TsSeCF3), enabling metal-free trifluoromethylselenolation of activated alkyl halides. Trifluoromethylselenolated compounds were obtained in moderate to excellent yields under optimized reaction conditions. Finally, cyclic voltammetric and F-19 NMR studies were conducted to gain insight into the reaction mechanism.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Sylvain Charvet, Maurice Medebielle, Julien C. Vantourout
Summary: This article presents a systematic study of the manganese-mediated alpha-radical addition of carbonyl groups to olefins. Through optimization of conditions and development of a practical electrocatalytic reaction, the scope of the reaction was expanded and a predictive model was established.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Taline Kerackian, Didier Bouyssi, Guillaume Pilet, Maurice Medebielle, Nuno Monteiro, Julien C. Vantourout, Abderrahmane Amgoune
Summary: This article describes the development and in-depth study of a cross-electrophile coupling of alkyl N-acyl imides with alkyl halides using nickel catalysis and electrochemistry. The method utilizes the stability and easy access of N-acyl imides to selectively synthesize dissymmetric dialkyl ketones. Mechanistic studies reveal the generation of alkyl radicals through single-electron oxidation of alkyl bromides by electrogenerated (bpy)Ni(I) species. The reaction of alkyl N-acyl imides with (bpy)Ni(0) and (bpy)Ni(I) species leads to Ni(II) acyl intermediates. A comprehensive mechanistic picture of this selective cross-electrophile coupling is achieved through these investigations.
Article
Chemistry, Medicinal
Nicolas Chopin, Julien Bosson, Shinya Iikawa, Stephane Picot, Anne-Lise Bienvenu, Adeline Lavoignat, Guillaume Bonnot, Mickael Riou, Corinne Beauge, Vanaique Guillory, Christophe Biot, Guillaume Pilet, Matthieu Chesse, Elisabeth Davioud-Charvet, Mourad Elhabiri, Jean-Philippe Bouillon, Maurice Medebielle
Summary: A series of ferrocenyl-containing gamma-hydroxy-gamma-lactam tetramates were prepared through a ring opening-ring closure process in the presence of ferrocenyl alkylamines. These compounds exhibited good antiplasmodial activity and selective antiparasitic activity.
EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY
(2022)
Article
Chemistry, Organic
Anais Loison, Gilles Hanquet, Fabien Toulgoat, Thierry Billard, Armen Panossian, Frederic R. Leroux
Summary: In this study, we report the in situ generation of a novel intermediate, difluoromethoxylated ketenimines, obtained from the corresponding oxime through a Beckmann rearrangement. The reactivity potential of this intermediate is demonstrated as it easily undergoes addition reactions with various nucleophiles. The broad applicability of this transformation leads to a chemical library of original molecules bearing -OCHF2, an Emergent Fluorinated Group (EFG).
Article
Chemistry, Organic
Yuki Hayashi, Yusuke Ishigaki, Jeremy Merad, Takanori Suzuki, Maurice Medebielle
Summary: The Bis[4-methoxy-5-methylenefuran-2(5H)-one]-type electron acceptors prepared in this study exhibit reversible electrochemical reduction, indicating the potential of 5-arylidenetetronate as an electrophore for developing novel electron acceptors.
Article
Chemistry, Organic
Fuying Zhu, Yamei Lin
Summary: In this study, a low-metal iron-supported catalyst (Fe20/NC-Mg) was reported for the efficient synthesis of quinoxaline compounds, using water as a solvent and without additional bases. The synergistic effect of FeNx site and Mg (OH)2 nanorods in the catalyst played a key role in achieving high yields (82-91%) in 16 examples. The gram-level synthesis and reusability of the catalysts after four cycles demonstrated its industrial application potential.
Article
Chemistry, Organic
Mikhail Kozlov, Alexey Tyurin, Andrey Dmitrenok, Vyacheslav Rusak, Aleksander Fedorov, Igor Zavarzin, Yulia Volkova
Summary: This study presents a novel and practical synthesis method for phosphorus-substituted 1,3,4-thiadiazolines using phosphorylthioformic acid hydrazides and ketones. The protocol demonstrates operational simplicity, availability of reagents, and tolerance towards different functional groups.
Article
Chemistry, Organic
Jisna Jose, Thomas Mathew
Summary: 2-Cyclopentenone and its derivatives are highly esteemed synthetic intermediates with exceptional utility in organic synthesis. They are favored structural motifs in numerous pharmaceutical drugs and natural products, highlighting their significance. The review discusses the various methods used to synthesize cyclopentenones from 2016 to 2023.
