Article
Chemistry, Organic
Jianxin Hou, Xue Han, Yiyi Zhang, Jiahui Huang, Jiawei Wang, Kedong Yuan
Summary: Triflic acid and silane can be used as a cooperative reductant to convert ketones into valuable products. This method is simpler compared to using precious-metal-based catalysts or complicated operational conditions. Protonated ketones can generate carbocations, allowing for the formation of Csp(2)-Csp(3) bonds with high reactivity and selectivity.
Article
Chemistry, Organic
Hui Yang, Yan Li, Wenhui Zhang, Jiayan Song, Jingyu Hu, Mengya Wang, Han Yao, Xia Xu, Na Li, Yanbo Yang, Rongrong Yu, Shuxia Xie, Cuiying Ye, Guo Wei
Summary: A novel regioselective hydrodeoxygenation method for alpha-diketones using phosphites as the deoxygenation reagent was achieved through visible-light photoredox catalysis. The method demonstrated a wide range of substrate compatibility and high functional group compatibility. Unsymmetric alpha-diketones were selectively reduced at the carbonyls of higher electrophilicity, providing a practical complementary approach for the monohydrodeoxygenation of alpha-diketones compared to existing methods.
Article
Chemistry, Organic
Joshua J. Clarke, Kevin Basemann, Neyen Romano, Stephen J. Lee, Michel R. Gagne
Summary: A novel diastereoselective, Lewis acid catalyzed 1,6-difunctionalization reaction of galactose and mannose derivatives has been developed using sequential nucleophile additions. The formation of a 3,6-anhydrosugar intermediate was found to be crucial for the 1,6-site-selectivity, and the reactivity of starting materials was influenced by the differences in basicity and stereoelectronic stabilization. The nucleophilicity parameter values of Mayr helped in predicting the most suitable reaction conditions for specific nucleophiles.
Article
Green & Sustainable Science & Technology
Fei Wang, Robert Pace, Yaying Ji, Jianchun Jiang, Xiaoxiang Jiang, Anna Krystianiak, Olivier Heintz, Gilles Caboche, Eduardo Santillan-Jimenez, Mark Crocker
Summary: In this study, the catalytic activity of Ni catalysts in the decarboxylation/decarbonylation of triglycerides to hydrocarbons was improved by employing Pd as a promoter and using multifunctional supports. Pd addition promoted Ni reduction, leading to an increase in the number of active sites. The use of SiO2-Al2O3 as a support further enhanced the catalyst performance by promoting Ni reduction, as well as providing a high surface area and strong acidity.
Article
Chemistry, Applied
William C. Spaller, Jennifer Q. Lu, Benjamin J. Stokes
Summary: In this study, a palladium-catalyzed deoxygenative transfer hydrogenation of ketones using B-2(OH)(4) as the sole additive was described. Deuterium labeling experiments with B-2(OD)(4) revealed that the incorporated protons exclusively originated from the diboron reagent. Spectroscopic evidence indicated the presence of a borate ester intermediate. This approach can be applied to deoxygenate various aromatic ketones.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Engineering, Environmental
Huan Su, Chao Shan, Xiaolin Zhang, Bingcai Pan
Summary: Chemical oxidation is essential in treating P(I)/P(III)-bearing wastewater. A low-cost catalyst, PdNi10, was developed as an alternative to the noble metal Pd for the chemical-free oxidation of P(I)/P(III) into P(V) by ambient O-2. PdNi10 demonstrated superior catalytic activity and wide applicability in the conversion of P(I) into P(V) under various pH conditions. The oxidation reactions were confirmed to be non-radical pathways, and the involvement of Ni components was found to be negligible. The reactive oxidant species for P(I)/P(III) oxidation were identified as interfacial OH groups resulting from H2O dissociation.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Chemistry, Physical
Qiu-Yue Nie, Zhen-Yu Ji, Yu Hu, Gong-Li Tang
Summary: Two reductases (TjhO5 and TjhD4) were identified to highly reduce the alpha,beta-unsaturated ketone of the D-ring in unconventional tetracyclines, completing the entire transformation via two distinct pathways involving different enzymatic mechanisms. TjhO5-mediated continuous reduction of C = O to CH2 possibly involved a distinctive deoxygenation mechanism. These findings highlight the unusual post-modification of tetracyclines and facilitate further engineering and biocatalysis to enrich the structural diversities.
Article
Chemistry, Organic
Brandon M. Young, Paolo Rossi, P. Jake Slavish, Yixin Cui, Munia Sowaileh, Jitendra Das, Charalampos G. Kalodimos, Zoran Rankovic
Summary: Isotopically labeled amino acids are commonly used for studying protein structure and dynamics by NMR. This study presents a facile gram-scale synthesis of compounds 1b and 2b under standard laboratory conditions from a common intermediate. The improved signal intensity with lower amounts of labeled precursor makes 1b and 2b potential alternatives to current labeling approaches.
Article
Chemistry, Inorganic & Nuclear
Neha Antil, Ajay Kumar, Naved Akhtar, Rajashree Newar, Wahida Begum, Kuntal Manna
Summary: A heterogeneous catalyst based on aluminum metal-organic framework and cobalt(II) hydride was reported for selective and efficient deoxygenation of a wide range of carbonyls and alcohols. The catalyst can be recycled and operates under ambient hydrogen pressure.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yanxin Wang, Kaiyue Yao, Duanjian Tao, Nian Xiang, Wei Wang, Zehui Zhang
Summary: In this study, Al2O3/nitrogen-doped carbon supported cobalt catalysts were prepared and investigated for the hydrodeoxygenation of sulfoxides into sulfides. The catalytic activity of the Co-NC/Al2O3-T catalysts was greatly influenced by the pyrolysis temperature, with Co-NC/Al2O3-500 showing excellent performance comparable to noble metal catalysts. Both the support and metallic cobalt nanoparticles played crucial roles in the catalyst's high activity, and the Co-NC/Al2O3-500 catalyst exhibited good stability after multiple runs.
REACTION CHEMISTRY & ENGINEERING
(2021)
Article
Chemistry, Multidisciplinary
Guangwu Sun, Herui Liu, Xiu Wang, Wenbo Zhang, Wenjun Miao, Qinyu Luo, Bing Gao, Jinbo Hu
Summary: In this manuscript, a novel palladium-catalyzed coupling reaction between gem-difluoroalkenes and aryl boronic acids is reported, which yields bioactive indane-type ketones with an all-carbon alpha-quaternary center. The mechanism involves a water-induced defluorination and cross-coupling cascade pathway, supported by characterization and stoichiometric reactions of the key intermediates RCF2PdII. The use of vinyl difluoromethylene motif as an in situ carbonyl precursor is unprecedented in transition-metal-catalyzed coupling reactions, and it is expected to spark broad interest in ketone synthesis, fluoroalkene functionalization, and design of new synthetic protocols based on the unique reactivity of difluoroalkyl palladium(II) species.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Oliver P. Williams, Alyah F. Chmiel, Myriam Mikhael, Desiree M. Bates, Charles S. Yeung, Zachary K. Wickens
Summary: In this study, a practical protocol for removing alcohol functional groups through reductive cleavage of their benzoate ester analogs is described. The transformation requires a strong single electron transfer (SET) reductant and a method to accelerate slow fragmentation after substrate reduction. A photocatalytic system was developed to generate a potent reductant from formate salts with Bronsted or Lewis acids that promote fragmentation. This deoxygenation procedure is effective for diverse alcohols and enables various transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Jabir Khan, Aparna Tyagi, Dibyajyoti Ghosh, Chinmoy Kumar Hazra
Summary: Due to the significance of carbon-heteroatom bonds in synthetic organic chemistry and pharmaceuticals, developing catalyst-free methods for their construction is an important goal in modern chemistry. This study presents an efficient HFIP-assisted direct reductive coupling of carbonyl compounds with nucleophiles, using Me2SiClH as a mild reducing agent. The protocol is practical, straightforward, and scalable, with broad substrate scope and high functional group compatibility. Additionally, a mechanism for this coupling reaction has been proposed based on control experiments and computational simulations.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Zhi-Yong Zeng, Jin-Xi Liao, Zhen-Ni Hu, De-Yong Liu, Qing-Ju Zhang, Jian-Song Sun
Summary: A chemical synthesis protocol for quillaic acid was established using easily available protoescigenin as a starting material, featuring scalability and robustness in each step. The devised protocol also demonstrated outstanding flexibility, allowing for convenient access to other scarce and difficult-to-access oleanane-type aglycones by sharing common intermediates with quillaic acid.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Caleb A. H. Jones, Nathan D. Schley
Summary: The cleavage of alkyl ethers by hydrosilylation is demonstrated with stability of O-aryl glycosides under iridium- and borane-catalyzed conditions. A cationic bis(phosphine)iridium complex catalyzes the selective 3-demethylation of various 2,3,4-tri-O-methyl pyranoses.
CHEMICAL COMMUNICATIONS
(2021)
Review
Chemistry, Organic
Weigang Fan, Charlie Verrier, Yves Queneau, Florence Popowycz
CURRENT ORGANIC SYNTHESIS
(2019)
Article
Chemistry, Organic
Florian Bahe, Lucie Grand, Elise Cartier, Maiwenn Jacolot, Sylvie Moebs-Sanchez, Daniel Portinha, Etienne Fleury, Florence Popowycz
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Organic
Rafael da Rosa, Lucie Grand, Eloir P. Schenkel, Lilian Sibelle Campos Bernardes, Maiwenn Jacolot, Florence Popowycz
Summary: 5-Hydroxymethylfurfural (5-HMF) is a renewable platform chemical used for obtaining various fine chemicals. This letter reports the synthesis of 5-HMF-based oxazole compounds, with a developed palladium-catalyzed procedure used to overcome challenges in preparing derivatives containing electron-withdrawing substituents.
Article
Chemistry, Organic
Johal Ruiz, Philippe Oger, Laurent Soulere, Florence Popowycz
Summary: Starting from commercially available (R)- and (S)-beta-citronellol, two strategies were designed to synthesize all four stereoisomers of 2,6-dimethyloctane monoterpene chirons in four or five steps in 32-47% overall yield. Key Ru-catalyzed asymmetric olefin hydrogenation step under moderate conditions allowed the obtainment of desired fragments. DM-SEGPHOS was identified as a economically advantageous alternative to H8-BINAP for equal performances in catalyst screening, opening up new possibilities for versatile and scalable syntheses of these useful building blocks.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Astronomy & Astrophysics
Michele Fiore, Carolina Chieffo, Augustin Lopez, Dimitri Fayolle, Johal Ruiz, Laurent Soulere, Philippe Oger, Emiliano Altamura, Florence Popowycz, Rene Buchet
Summary: Phospholipids are crucial components of biological membranes and play roles in cell signaling, enzymatic reactions, and energy metabolism. They also have significant implications in the emergence of life. Recent advancements have provided a deeper understanding of these unique hydrophobic molecules and their essential functions in cell biology. There is now growing interest in prebiotic lipidomics, calling for a reevaluation of these important biomolecules.
Article
Biochemistry & Molecular Biology
Rafael da Rosa, Bibiana Paula Dambros, Milene Hoehr de Moraes, Lucie Grand, Maiwenn Jacolot, Florence Popowycz, Mario Steindel, Eloir Paulo Schenkel, Lilian Sibelle Campos Bernardes
Summary: Chemical scaffolds of natural products serve as inspiration for the development of novel molecules. In this study, we designed and synthesized 46 synthetic derivatives based on the structure of tetrahydrofuran lignans and oxazole alkaloids, and screened them for activity against T. cruzi. Several compounds showed activity and inhibitory effects on the parasite.
BIOORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Maiwenn Pineau, Shiny B. Martis, Raphael Forquet, Jessica Baude, Camille Villard, Lucie Grand, Florence Popowycz, Laurent Soulere, Florence Hommais, William Nasser, Sylvie Reverchon, Sam Meyer
Summary: DNA supercoiling is a crucial mechanism in bacterial chromosome compaction, which is regulated by specific topoisomerases, physiological conditions, and genomic context. The altered supercoiling level leads to changes in global gene expression in bacteria.
NUCLEIC ACIDS RESEARCH
(2022)
Article
Biochemistry & Molecular Biology
Thomas Chetot, Xavier Serfaty, Lena Carret, Alexandre Kriznik, Sophie-Rahueal-Clermont, Lucie Grand, Maiwenn Jacolot, Florence Popowycz, Etienne Benoit, Veronique Lambert, Virginie Lattard
Summary: Four coding splice variants of Pdi pre-mRNA were discovered in rats. The consensus sequence and the third splice variant were found to be fully active, while the second splice variant was less active than the consensus sequence.
BIOCHIMICA ET BIOPHYSICA ACTA-GENERAL SUBJECTS
(2023)
Article
Chemistry, Organic
Grand Lucie, Powderly Marian, Popowycz Florence, Jacolot Maiwenn
Summary: The regio- and diastereoselective synthesis of chiral amines derived from 1,4-D-sorbitan has been achieved through the borrowing hydrogen reaction, using a cooperative catalysis between an achiral iridium catalyst and diphenylphosphoric acid. The differential reactivities of the four hydroxyl groups on the 1,4-D-sorbitan scaffold have also been emphasized.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Jingjing Jiang, Yves Queneau, Florence Popowycz
Summary: The use of the renewable platform molecule 5-HMF in multi-component reaction with a diamine and an alkynone to generate seven-membered 1,5-benzodiazepines is described. Ammonium acetate in ethanol proved to be a clean and efficient system among catalysts/solvents couples. The optimized conditions were used to investigate the scope of the reaction providing a library of 1,5-benzodiazepines in moderate to good yields from a wide range of diversely substituted diamines and alkynones or alkyl alkynoates.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Malvina Larduinat, Jordan Franc, Maiwenn Jacolot, Florence Popowycz
Summary: In this study, the Ir(III)-catalyzed synthesis of 3-pyrrolidinols and 4-piperidinols by reacting 1,2,4-butanetriol or 1,3,5-pentanetriol with primary amines was demonstrated. This borrowing hydrogen methodology was also applied to the sequential diamination of triols, leading to the formation of amino-pyrrolidines and aminopiperidines.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Nolan Chatron, Manon Boulven, Adrien Montagut-Romans, Flavien Ponsot, Maiwenn Jacolot, Herve Caruel, Etienne Benoit, Florence Popowycz, Virginie Lattard
Summary: Vitamin K antagonists (VKAs) have been widely used as anticoagulants, but resistance to these drugs due to VKORC1 mutations has been a challenge. In this study, the crystal structure of VKORC1 provided new insights for the development of new anticoagulants. By combining chemical synthesis, enzymatic assays and molecular modelling, a structure-activity relationship model was established, showing that lipophilicity, membrane permeability and affinity towards human VKORC1 enzyme are key factors for potent anticoagulants.
BIOORGANIC & MEDICINAL CHEMISTRY
(2023)
Article
Chemistry, Organic
Jordan Francois, Jordan Rio, Erwann Jeanneau, Marie-Eve L. Perrin, Maiwenn Jacolot, Pierre-Adrien Payard, Florence Popowycz
Summary: Taking advantage of our preliminary observations, we successfully achieved the direct C-C borrowing hydrogen functionalization on isosorbide using an Ir-based organometallic homogeneous catalyst with excellent diastereocontrol. The reaction involves a catalytic dehydrogenation, in situ aldol condensation/crotonisation, and a catalytic dehydrogenation to yield the desired homologated product. Through a computational mechanistic investigation, we elucidated the stereoelectronic effects and the roles of the Na counter-cation in guiding the hydride addition and coordinating the substrate's oxygen atoms, thus rationalizing the experimental selectivity at the molecular level.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
Johal Ruiz, Josephine G. LoRicco, Laurent Soulere, Marta Salvador Castell, Axelle Grelard, Brice Kauffmann, Erick J. Dufourc, Bruno Deme, Florence Popowycz, Judith Peters
Summary: Archaeal membrane lipids have unique structures that enable them to withstand extreme temperature and pressure conditions. A study on the synthesis of an archaeal lipid called 1,2-di-O-phytanyl-sn-glycero-3-phosphoinositol (DoPhPI) derived from myo-inositol reveals its resistance mechanisms. The experiments show that DoPhPI and DoPhPC can form small vesicles in aqueous dispersions, and these dispersions undergo phase transitions from lamellar to cubic and hexagonal phases with increasing temperature. The phytanyl chains in the lipid also contribute to the bilayer's dynamic properties over a wide temperature range. These findings suggest that the unique properties of archaeal lipids provide plasticity and aid in resisting extreme conditions.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Review
Chemistry, Organic
Jing Xu, Weigang Fan, Florence Popowycz, Yves Queneau, Yanlong Gu
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2019)
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.
