Article
Chemistry, Organic
Jordi Mestre, Isabel Bascuas, Miguel Bernus, Sergio Castillon, Omar Boutureira
Summary: Fluorinated carbohydrate mimetics are important in Glycoscience, but the synthesis of complex C(sp(3))-CF3 congeners is underdeveloped. A new protocol for preparing 2-deoxy-2-trifluoromethyl-d-hexopyranosides from d-glycals is presented. The stereoselectivity of glycosylation is mainly controlled by electronic and steric factors, resulting in the formation of 1,2-trans glycosides due to the configuration of the CF3 moiety at C-2. This approach was successfully applied in the synthesis of 2-CF3-glycoconjugates of natural origin.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Materials Science, Ceramics
Jaeyeop Chung, Hiroyuki Inoue, Kohei Yoshimoto, Atsunobu Masuno, Yasuhiro Watanabe
Summary: Substituting oxygen with fluorine in oxyfluoride glasses can decrease the glass-transition temperature and onset crystallization temperature, maximizing the glass-forming ability. The increase in fluorine content raises the atomic packing densities of the glasses, altering their absorption edge and transparency while improving optical properties.
JOURNAL OF THE AMERICAN CERAMIC SOCIETY
(2021)
Article
Chemistry, Organic
Shouxiong Chen, Hui Wang, Qi Lin, Zhiqiang Weng
Summary: A new protocol has been developed for the synthesis of diversely substituted 2-trifluoromethyl chromenes via the cyclization reaction of o-isopropenylphenols with trifluoroacetic anhydride. This methodology shows good functional group tolerance and allows for derivatization of the product to obtain other valuable scaffolds.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Polina A. Fomitskaya, Dmitry A. Argunov, Yury E. Tsvetkov, Andrey Lalov, Nadezhda E. Ustyuzhanina, Nikolay E. Nifantiev
Summary: The study focused on the effect of reaction conditions on heterogeneous azidophenylselenylation (APS) of 3,4,6-tri-O-acetyl-d-galactal, resulting in reliable preparation of phenyl 2-azido-2-deoxy-1-seleno-alpha-d-galactopyranoside triacetate in high yield. Additionally, acetoxyphenylselenylation was shown to be a convenient method for synthesizing 1-O-acetyl-2-seleno-2-deoxy derivatives, valuable intermediates in the chemistry of 2-deoxysugars. The detailed characterization of 2-seleno-2-deoxy sugars by NMR data, including Se-77 chemical shifts and (n)J(Se-H) coupling constant values, provided further insights into their properties.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Biochemistry & Molecular Biology
Xueying You, Yifei Cai, Chenyu Xiao, Lijuan Ma, Yong Wei, Tianpeng Xie, Lei Chen, Hui Yao
Summary: An effective and direct methodology using AgOTf as a catalyst has been developed for the stereoselective synthesis of alpha-2-deoxythioglycosides. This method not only allows the synthesis of disaccharides, but also enables successful late-stage glycosylation of estrogen, L-menthol, and zingerone with thiol compounds.
Article
Chemistry, Medicinal
Benoit Laleu, Yuichiro Akao, Atsuko Ochida, Sandra Duffy, Leonardo Lucantoni, David M. Shackleford, Gong Chen, Kasiram Katneni, Francis C. K. Chiu, Karen L. White, Xue Chen, Angelika Sturm, Koen J. Dechering, Benigno Crespo, Laura M. Sanz, Binglin Wang, Sergio Wittlin, Susan A. Charman, Vicky M. Avery, Nobuo Cho, Masahiro Kamaura
Summary: A novel antimalarial scaffold was discovered through a phenotypic high-throughput screen, with a potent inhibitor 19f identified as 95-fold more potent than the original hit compound. Profiling of 19f showed a fast in vitro killing profile, and its in vivo activity in a murine model of human malaria was dose-dependent, providing a concomitant benefit.
JOURNAL OF MEDICINAL CHEMISTRY
(2021)
Article
Chemistry, Organic
Irshad Ahmad Zargar, Norein Sakander, Debaraj Mukherjee
Summary: A strategy was designed for the synthesis of regioselective and stereoselective displacement of C-3 acetate group in the presence of other C-4 and C-6 acetate of 2-ketophenyl-glycal by different aromatic and cyclic aliphatic thiol nucleophiles, inspired by cytosolic esterase mediated thiolation of glucosamine sugars. The protocol achieved the removal of C-3 acetate group and maintained high axial selectivity, resulting in a library of 3-arylthiosugars with excellent yields. This stereoselective approach showed tolerance to different ester-protected glycals and thiophenols, aliphatic cyclic thiols, and mercaptans. Control experiments were conducted to establish the mechanism and reason behind the stereoselectivity.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Plant Sciences
Eleonora Cataldo, Linda Salvi, Giovan Battista Mattii
Summary: The study highlights the impact of water stress on grapevine growth and quality characteristics, resulting in reduced yield and lower wine quality. By observing the ecophysiology and technological maturity of vineyards under different irrigation treatments, it was found that vines under well watered conditions performed better, accumulating more thiol precursors.
PLANT PHYSIOLOGY AND BIOCHEMISTRY
(2021)
Article
Chemistry, Organic
Bryant Pero, Mark W. Peczuh
Summary: A new synthesis of carbohydrate-based oxepines using 2,3;4,6-di-O-acetonide mannose as a key starting material is reported. The oxepine is an important precursor used in the synthesis of septanose glycomimetics of mannopyranosides.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Thermodynamics
Junfeng Bai, Yuxiang Zhu, Chong-Wen Zhou, Guillaume Dayma, Zeynep Serinyel, Philippe Dagaut
Summary: Theoretical investigations were conducted on the kinetics of pentan-2-ol radical decomposition and isomerization reactions, along with thermochemistry data calculations for key species involved. The study found that 1-pentene and 2-pentene are important bimolecular products.
PROCEEDINGS OF THE COMBUSTION INSTITUTE
(2021)
Article
Biochemistry & Molecular Biology
Aleksandra Tracz, Martyna Malinowska, Stanislaw Lesniak, Anna Zawisza
Summary: A concise synthetic route to achieve stereoselective access to C-glycosyl-aminoethyl sulfide derivatives has been developed. This was achieved through the reaction of tributhyltin derivatives of glycals with aziridinecarboaldehyde and the regioselective ring opening of a chiral aziridine with thiophenol. The absolute configurations of the resulting diastereoisomers were determined by 1H NMR spectroscopy.
Article
Chemistry, Multidisciplinary
Pradip Das, Mosidur Rahaman Molla, Amit Kumar, Rima Thakur
Summary: The study reports an efficient and stereoselective synthesis of 2,3-dideoxy-beta-O-glycosides from C3-(o-cyanobenzoate) ester protected glycal donors via Ferrier rearrangement under Pd(0)-catalyzed Tsuji-Trost conditions. The stereo-chemical outcome of the reactions was independent of the nature of protecting groups or conformational flexibility of the glycal donors. Incorporation of the directing group on the benzoate ester altered the reactivity for Tsuji-Trost as well as Ferrier Rearrangement pathway.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Thermodynamics
Joanna Drzezdzon, Barbara Gawdzik, Przemyslaw Rybinski, Jacek Malinowski, Dagmara Jacewicz
Summary: The thermal stability of oligomers produced using 2-chloro-2-propen-1-ol as the monomer was studied in this research. The oligomers were synthesized with chromium(III) and oxovanadium(IV) complexes as catalysts, activated by modified methylaluminoxane (MMAO-12). The study used thermal gravimetry and differential scanning calorimetry to determine the glass transition temperatures and thermal stability of the oligomers based on the central catalyst cations Cr(3+) and V(4+).
JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY
(2021)
Article
Chemistry, Organic
Vasiliy M. Muzalevskiy, Zoia A. Sizova, Valentine G. Nenajdenko
Summary: The reaction of alpha-CF3-beta-(2-nitroaryl)enamines with benzaldehydes resulted in the synthesis of nitro-substituted alpha,beta-diaryl-CF3-enones in high yield. Subsequent reduction of the nitro-group to the amino moiety followed by intramolecular cyclization generated a 5-membered hemiaminal that could react with various nucleophiles to yield functionalized 2-CF3-indoles. The high efficiency and broad synthetic scope of the reactions were demonstrated, and a possible mechanism was discussed.
Article
Chemistry, Organic
Wei Wu, Shunli Wen, Xinyu Zhang, Qi Lin, Zhiqiang Weng
Summary: A highly efficient and regioselective synthesis of highly substituted 2-trifluoromethyl pyrrole derivatives is reported via a silver-catalyzed cyclization of vinyl azides with ethyl 4,4,4-trifluoro-3-oxobutanoate. Various types of alpha-(heteo)aryl, alkyl, alpha-aryl, and alpha,beta-disubstituted vinyl azides can participate in this transformation. The proposed reaction mechanism involves the addition of in situ generated 2H-azirine to the diketone species, followed by intramolecular addition, N-C-1 cleavage, and elimination.
Article
Engineering, Environmental
Jose Delgado, Wenel Naudy Vasquez Salcedo, Giulia Bronzetti, Valeria Casson Moreno, Melanie Mignot, Julien Legros, Christoph Held, Henrik Grenman, Sebastien Leveneur
Summary: The research focuses on the hydrogenation of levulinic acid and butyl levulinate over Ru/C and Amberlite IR-120, evaluating different kinetic models to describe the system. This study fills the gap in the literature by examining the simultaneous hydrogenation of LA and AL in one-pot.
CHEMICAL ENGINEERING JOURNAL
(2022)
Review
Chemistry, Multidisciplinary
Valmir B. Silva, Yane H. Santos, Renata Hellinger, Sergui Mansour, Antonin Delaune, Julien Legros, Sergey Zinoviev, Evandro S. Nogueira, Elisa S. Orth
Summary: This review highlights the contributions of green chemistry in the field of organophosphorus compounds, including advancements in synthesis, decontamination, and detection. New technologies such as the use of catalysts and continuous flow systems are proving to be safer and more efficient in handling these chemicals.
Article
Chemistry, Multidisciplinary
Tingting Cao, Benoit Crousse
Summary: A new family of fluorinated sulfonyl hydrazides has been synthesized from accessible and cheap sulfinates and azodicarboxylates. Additionally, trifluoromethylsulfonyl hydrazide (Tf(Boc)N-NHBoc) serves as an effective source of SCF3 in the sulfenylation of indoles.
HELVETICA CHIMICA ACTA
(2022)
Article
Chemistry, Physical
Sondes Ghrairi, Pascal Retailleau, Benoit Crousse, Thouraya Barhoumi Slimi
Summary: A one-pot synthesis method was used to generate variously substituted gamma-chloro-gamma, ,beta-allylic carbamates from ,beta-chloro-alpha, ,beta-unsaturated aldehydes. The synthesized carbamates and their corresponding intermediates, gamma-chloro-gamma, ,beta-allylic alcohols, were characterized using spectroscopic techniques such as (H-1 and C-13) NMR, IR and HRMS. The crystal structures of two allylic carbamates were determined using single crystal X-ray diffraction.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Chemistry, Multidisciplinary
Maxime Manneveau, Batoul Rkein, Dominique Cahard, Julien Legros, Isabelle Chataigner
Summary: This study demonstrates that indoles substituted by electron-depleted thio groups at positions 1 and 3 can react as C2 = C3 dipolarophiles with an electron-rich azomethine ylide dipole under flow conditions, leading to dearomatizing (3 + 2) cycloadditions to afford the corresponding fluorinated 3D-pyrrolidinoindolines bearing a tetrasubstituted carbon centre at the ring junction.
JOURNAL OF FLOW CHEMISTRY
(2022)
Article
Chemistry, Physical
Marcel Klinksiek, Sindi Baco, Sebastien Leveneur, Julien Legros, Christoph Held
Summary: The solvent plays a crucial role in biomass conversion by influencing dissolution, reaction kinetics, catalyst activity, and thermodynamic equilibrium. This study used the advanced thermodynamic model ePC-SAFT to predict the activities of reactants and catalyst in the acid-catalyzed esterification of levulinic acid (LA) with ethanol. By simultaneously solving the dissociation equilibrium of the catalyst and relating reaction kinetics to proton activity, the influence of the catalyst on kinetics was successfully predicted.
Article
Chemistry, Multidisciplinary
Maria Ivanova, Thomas Poisson, Philippe Jubault, Julien Legros
Summary: This article describes the continuous flow synthesis of six benzodiazepines from aminobenzophenones, including diazepam, fludiazepam, nordazepam, nitrazepam, clonazepam, and oxazepam.
JOURNAL OF FLOW CHEMISTRY
(2023)
Article
Engineering, Environmental
Alexandre Cordier, Marcel Klinksiek, Christoph Held, Julien Legros, Sebastien Leveneur
Summary: The use of enzymes for chemical reactions has increased in recent years, leading to the development of various models to describe their kinetics. The Michaelis-Menten model is commonly used for reactions with only one substrate, while more complex models like the Ping-Pong Bi-Bi model are needed for bimolecular systems like esterification. These advanced models are crucial for scaling up reactors and optimizing production. However, these models typically do not take into account the reaction temperature.
CHEMICAL ENGINEERING JOURNAL
(2023)
Editorial Material
Biochemical Research Methods
Jean-Christophe M. Monbaliu, Julien Legros
Summary: The traditional paradigm of centralized, stepwise, large-scale chemical production has weaknesses and threats that are unsustainable. The emerging technology of microreactors offers a solution to these issues and enables safer and more reliable chemical production.
Article
Chemistry, Multidisciplinary
Katia Perez, Sebastien Leveneur, Fabrice Burel, Julien Legros, Daniela Vuluga
Summary: In this study, the anionic polymerization of myrcene in a microflow reactor was successfully achieved, yielding low molar mass polymyrcene. Carbon dioxide was introduced to modify the polymerization product with carboxylic acid functional groups. A kinetic model was developed to accurately predict the outcome of the polymerization under such flow conditions.
REACTION CHEMISTRY & ENGINEERING
(2023)
Review
Chemistry, Multidisciplinary
Benoit Crousse
Summary: This review provides an overview of the synthetic routes of the N-CF3 group, including desulfurization reactions and electrophilic and radical trifluoromethylations. The article also discusses the valorization of N-CF3 compounds and presents the results of metabolic stability studies.
Article
Chemistry, Organic
Yazid Boutahri, Khoubaib Ben Haj Salah, Nicolas Tisserand, Nathalie Lensen, Benoit Crousse, Thierry Brigaud
Summary: The straightforward synthesis of chiral (R)- and (S)-difluoroalanine is reported, which involves a Strecker-type reaction followed by other steps. Diastereomerically pure tripeptides are obtained through peptide coupling reactions. The hydrophobic contribution of difluoroalanine in a peptide chain is found to be similar to that of isoleucine for a smaller side chain volume.
Article
Chemistry, Multidisciplinary
Maxime Boddaert, Pauline Bianchi, Diana V. Silva-Brenes, Ancuta Musina, Marc Winter, Philippe M. C. Roth, Pierre-Yves Renard, Julien Legros, Jean-Christophe M. Monbaliu
Summary: This study introduces a new, efficient, safe, and sustainable flow protocol using ozone to oxidatively neutralize sulfur-based chemical warfare agent simulants. The combination of computational research and experimental validation has successfully achieved rapid neutralization under flow conditions.
Article
Chemistry, Organic
Jose Laxio Arenas, Pascal Retailleau, Jean-Michel Gillet, Nour-Eddine Ghermani, Sandrine Ongeri, Benoit Crousse
Summary: The 5-fluoro triazole amino acid scaffold prepared by halogen exchange was successfully incorporated into peptides. The X-ray diffraction results revealed an important localization of the 5-fluoro triazole motif on one side of the negative potential surface, with the fluorine atom showing a cylindrical shape in its electron density deformation.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Victor-Emmanuel H. Kassin, Diana Silva-Brenes, Thomas Bernard, Julien Legros, Jean-Christophe M. Monbaliu
Summary: This study reports the development of a continuous flow generator that produces highly reactive organic hypochlorites for the chemical neutralization of sulfur-based chemical warfare agent (CWA) simulants. The generator uses low environmental footprint resources and equipment, as well as widely available and cheap chemicals. The new neutralization protocol offers flexibility and efficiency.
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.
