Article
Chemistry, Organic
Guenter Haufe
Summary: This review highlights the significant progress made in the past few decades in the application of pentafluorosulfanyl (SF5) group in organic compounds, focusing on the synthesis of SF5-containing small building blocks using SF5X reagents and their potential applications in drug and pesticide design as well as materials sciences.
Article
Chemistry, Inorganic & Nuclear
Vincent Mastalerz, Kevin Lam, Jean-Francois Paquin
Summary: The study explored a Kolbe-based reaction for the preparation of aliphatic SF5-compounds. Using 2-(pentafluoro-lambda 6-sulfanyl)acetic acid as the SF5CH2 source, it reacted with aliphatic carboxylic acid. Nine examples of unsymmetrical coupling were achieved, with NMR yields ranging from 15% to 66% (up to 62% isolated yield). Although the yields are modest, this method represents one of the few strategies to rapidly access aliphatic SF5-containing compounds.
JOURNAL OF FLUORINE CHEMISTRY
(2023)
Article
Chemistry, Organic
Katsumi Maeda, Ryosuke Matsubara, Masahiko Hayashi
Summary: The synthesis of anilines and indoles from cyclohexanones using a Pd/C-ethylene system was successfully achieved under nonaerobic conditions with a simple combination of NH4OAc and K2CO3. The desired products were generated through hydrogen transfer between cyclohexanone and ethylene, with the reaction tolerating a variety of substitutions on the starting cyclohexanones.
Article
Chemistry, Organic
Lin Wang, Shengyang Ni, Josep Cornella
Summary: This manuscript describes the oxidative fluorination of aryl phosphorothiolates to access Ar-SF4Cl compounds, which are precursors for the highly coveted Ar-SF5 compounds. The protocol has been demonstrated for >10 examples and showed good tolerance to various functional groups. Additionally, AgBF4 was shown to be an effective fluorinating agent for yielding Ar-SF5 compounds.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Physical
Rusi Peng, Huang Pan, Xintong Li, Shaoqing Jin, Zhendong Wang, Jingang Jiang, Weimin Yang, Hao Xu, Peng Wu
Summary: A novel and efficient strategy is developed to post-synthesize Ti-MSE catalysts by combining interzeolite transformation, dealumination, and isomorphous substitution of Ti. The resulting catalyst exhibits high catalytic activity and para-selectivity in anisole hydroxylation, possibly due to the strong interaction between the framework hydroxyls in Ti-MSE and the oxygen-containing substituent groups in aromatic substrates.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Organic
Matthew C. Carson, Brandon J. Orzolek, Marisa C. Kozlowski
Summary: A photocatalytic method for selectively synthesizing 4-hydroperoxy-2,5-cyclohexadienones from para-alkyl phenols with yields ranging from 27% to 99% was reported. By utilizing this approach, (+/-)-stemenone B and (+/-)-parvistilbine B were synthesized in 9 and 11 steps, respectively, from commercially available starting materials. Furthermore, the influence of base and solvent on selectivity was investigated, providing insights into the mechanism of this transformation.
Article
Chemistry, Organic
Matthew W. Halloran, Elizabeth Li, Kenneth Virgel N. Esguerra, Jean-Philip Lumb
Summary: Here, a bioinspired approach to the synthesis of 1,4-benzothiazines is reported, drawing inspiration from pheomelanin pigments biosynthesis. General conditions for the regioselective coupling reaction between ortho-quinones and thiols were developed. The mild conditions allowed for a wide range of thiol and ortho-quinone coupling partners with suppression of redox-exchange.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Xu Chen, Anjun Qin, Ben Zhong Tang
Summary: A regio-selective and atom-economical spontaneous multicomponent polymerization was established, using CS2 as a catalyst to link activated internal alkynes and amine monomers into polymer chains. The resulting polymers exhibited exceptional optical characteristics and good film-forming capabilities, while being synthesized in a green and efficient manner with low energy consumption, minimized waste generation, and efficient use of CS2 resources.
Article
Chemistry, Multidisciplinary
Jiang Liu, Jingcheng Xu, Haibo Mei, Jianlin Han
Summary: An efficient electrochemical transition-metal-free strategy has been developed for the difunctionalization of alkenes to construct beta-alkoxyl sulfonate esters through C-S, S-O, and C-O bond formation. This strategy offers mild reaction conditions, easy-to-handle reactants, and good chemical yields, providing a green and easy access to sulfonate esters.
Article
Chemistry, Applied
Yuxing Tan, Wujiu Jiang, Penghui Ni, Yang Fu, Qiuping Ding
Summary: A strategy for the synthesis of quinazolines via elemental sulfur-mediated oxidative condensation of nitriles and 2-(aminomethyl)anilines was developed. This metal-/solvent-free reaction tolerates a wide range of functional groups and provides the corresponding products in high yield, making it suitable for gram-scale reactions. The photophysical properties of several product derivatives were studied through UV/Vis absorption and fluorescence spectra analysis.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Applied
N. S. Nesterov, A. A. Smirnov, V. P. Pakharukova, V. A. Yakovlev, O. N. Martyanov
Summary: NiCu-containing catalysts stabilized by SiO2 with different metals ratio were prepared using green supercritical antisolvent precipitation method, leading to highly loaded dispersed metal catalysts; the main product of the hydrodeoxygenation process over these catalysts was cyclohexane.
Article
Chemistry, Organic
Gangqi Peng, Hao Cheng, Xiya Cheng, Yang He, Yuanyuan An, Jie Wu, Danqing Zheng
Summary: A reductive Sandmeyer-type sulfinylation reaction of aryldiazonium salts with sodium sulfinates was developed, which proceeds under photocatalysis and generates various sulfoxides of significant value via radical substitution pathway. The in situ diazotization of aromatic amines in a one-pot, two-step process also allows for the conversion to corresponding sulfoxides. The successful late-stage sulfinylation of drug-based amines further demonstrates the practicality of this method.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Energy & Fuels
Zhilin Xi, Ke Xi, Linping Lu, Mengmeng Zhang
Summary: The evolution mechanism of organic sulfur in the process of coal spontaneous combustion was investigated through quantum chemical calculations. The results showed that mercaptans play a dominant role in the oxidation process, and the oxidation of 2-methylthiophene releases the most heat.
Article
Chemistry, Organic
Wangzhi Yu, Jian Han, Dongmei Fang, Min Wang, Jian Liao
Summary: This method utilizes palladium catalysis to synthesize aliphatic thioesters with exclusive linear selectivity, achieving good to excellent yields (up to 91%) and demonstrating broad substrate scope, functional group tolerance, and practicality, showcasing its advantages for various applications.
Article
Chemistry, Multidisciplinary
Sheng Han, Ying Cheng, Shanshan Liu, Chaofu Tao, Aiping Wang, Wanguo Wei, Han Yu, Yongge Wei
Summary: The study reported a molybdenum oxide compound catalyzed selective oxidation of anilines with hydrogen peroxide as green oxidant, leading to the synthesis of aromatic azo compounds. The use of stoichiometric metal oxidants was avoided and fully selective synthesis of products was achieved. Preliminary mechanistic investigations suggested the intermediacy of highly active reactive and elusive Mo imido complexes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Kheironnesae Rahimidashaghoul, Iveta Klimankova, Martin Hubalek, Vaclav Matousek, Josef Filgas, Petr Slavicek, Tomas Slanina, Petr Beier
Summary: The study utilized different reagents for fluoroalkylation, with the photochemical process showing better selectivity. However, side reactions still occurred in the presence of cysteine residues.
Article
Chemistry, Applied
Athanasios Markos, Lukas Janecky, Tomas Chvojka, Tomas Martinek, Hector Martinez-Seara, Blanka Klepetarova, Petr Beier
Summary: This study presents a novel aluminum halide-mediated synthesis of N-haloalkenyl imidoyl halides, which is highly versatile and provides highly functionalized products. The reaction mechanism involves the opening of the triazole ring, N-2 elimination, and halide exchange reactions.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Olga Bakhanovich, Viktor Khutorianskyi, Vladimir Motornov, Petr Beier
Summary: The rhodium-catalyzed transannulation reaction between N-perfluoroalkyl-1,2,3-triazoles and aromatic or aliphatic terminal alkynes under microwave heating conditions selectively produced N-perfluoroalkyl-3,4-disubstituted pyrroles as major products and N-fluoroalkyl-2,4-disubstituted pyrroles as minor products. High selectivity was observed particularly in reactions involving aliphatic alkynes.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Athanasios Markos, Lukas Janecky, Blanka Klepetarova, Radek Pohl, Petr Beier
Summary: The study corrected the stereochemistry based on ge-1D ROESY NMR experiment and X-ray crystal structure analyses. By applying the reaction to N-fluoroalkyl-1,2,3-triazoles, new (Z)-beta-enamido fluorides were successfully synthesized in a stereoselective manner. A mechanism involving coordination of BF3 with the triazole ring, vinyl diazonium, and vinyl cation intermediates was proposed.
Article
Chemistry, Organic
Martin Posta, Vaclav Zima, Lenka Postova Slavetinska, Marika Matousova, Petr Beier
Summary: The synthesis of a sulfur-containing karrikin compound and a class of karrikin derivatives with sulfur heteroatoms incorporated into the core backbone is reported. Their biological activity in inhibiting acetylcholinesterase is evaluated.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Vladimir Motornov, Petr Beier
Summary: NH-1,2,3-Triazoles undergo ring cleavage in reactions with fluorinated acid anhydrides and can be used for the synthesis of fluoroalkylated compounds.
Article
Chemistry, Organic
Lukas Janecky, Athanasios Markos, Blanka Klepetar, Petr Beier
Summary: 4-Aryl-5-allyl-N-fluoroalkyl-1,2,3-triazoles were synthesized through a three-component reaction of fluoroalkyl azides, copper acetylides, and allyl halides. These compounds underwent aluminum halide-mediated transformation to N-(4-halo-2-aryl-cyclopentenyl) imidoyl halides by cyclization of vinyl cation intermediates, followed by halide capture. The cyclic products could be further utilized for the synthesis of N-alkenyl amides, amidines, isoquinolines, and tetrazoles, or for the subsequent modification of the cyclopentene ring.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Vladimir Motornov, Petr Beier
Summary: Metal-free cascade reaction of NH-1,2,3-triazoles with one-carbon electrophiles, such as thiophosgene and triphosgene, generates N-vinylated ring cleavage products. N-vinylisothiocyanates can be synthesized from NH-triazoles and thiophosgene using this approach. A variety of multifunctional compounds, such as N-vinylcarbamates, unsymmetrical vinylureas, carbamothioates, etc. were prepared by a one-pot method from NH-triazoles, triphosgene, and nucleophiles.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Mykyta Ziabko, Blanka Klepetarova, Petr Beier
Summary: A new stable fluorinated azide called azidodifluoromethylphenyl sulfone was synthesized from difluoromethyl phenyl sulfone on a multi-gram scale. This azide showed synthetic utility in the preparation of N-difluoro-(phenylsulfonyl)-methyl-1,2,3-triazoles through azide-alkyne cycloaddition reactions. It also served as a synthetic equivalent of the azidodifluoromethylanion.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Vladimir Motornov, Blanka Klepetarova, Petr Beier
Summary: High-valent Cu(III) trifluoromethyl complexes with 1,3-diketonates as bidentate oxygen donor ligands LCu(III)(CF3)(2) were synthesized and characterized. They exhibit bench stability and solubility in organic solvents. The reactivity of Cu(III) trifluoromethyl diketonates in radical and radical-polar crossover trifluoromethylation reactions was demonstrated, along with the direct C-H trifluoromethylation of electron-rich arenes and indoles and the azolo- and oxy-trifluoromethylation of terminal alkynes and aromatic thiol using LCu(III)(CF3)(2) under mild conditions.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Elena Shaitanova, Vaclav Matousek, Tadeas Herentin, Martin Adamec, Robert Matyas, Blanka Klepetarova, Petr Beier
Summary: This article introduces a new method for preparing fluorinated azidoethane and its application in various reactions.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Vladimir Motornov, Radek Pohl, Blanka Klepetarova, Petr Beier
Summary: Elusive N-acyl-1,2,3-triazoles formed by direct acylation of NH-1,2,3-triazoles were isolated and characterized. Thermodynamic N2 isomers were found to be preferred. Direct evidence of interconversion between N1- and N2-acyltriazoles confirmed their usefulness in denitrogenative transformations. An efficient synthesis of enamido triflates from NH-triazoles via N2-acyl-1,2,3-triazole intermediates was developed.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Anna Kubickova, Athanasios Markos, Svatava Voltrova, Anezka Markova, Josef Filgas, Blanka Klepetarova, Petr Slavicek, Petr Beier
Summary: N-Fluoroalkylated 1,2,3-triazoles undergo a microwave-heating-assisted ring opening, nitrogen molecule elimination, and concomitant group rearrangement to form isolable N-fluoroalkylketenimines. This reagent-free process exhibits a wide scope and high efficiency, providing a new route to unexplored N-fluoroalkyl compounds. Mechanistic and computational studies were employed to investigate the reaction mechanism. [2 + 2] cycloaddition of ketenimines with alkynes or alkenes yields novel cyclobutenimines and cyclobutanimines, respectively. Addition of oxygen, sulfur, and nitrogen nucleophiles to ketenimines gives rise to new N-fluoroalkyl imidates, thioimidates, and amidines.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Review
Chemistry, Multidisciplinary
Vladimir Motornov, Petr Beier
Summary: This review focuses on the utilization of NH-1,2,3-triazoles as easily accessible building blocks for denitrogenative ring cleavage transformations, providing multifunctionalized nitrogen heterocycles and N-alkenyl compounds. These processes offer a convenient route to a range of pharmaceutically relevant heterocyclic cores and N-alkenyl compounds by leveraging the ready availability of NH-1,2,3-triazoles. The synthetic usefulness of in situ acylated NH-1,2,3-triazoles as viable alternatives to widely explored N-sulfonyl-1,2,3-triazoles in ring cleavage processes is highlighted.
Article
Chemistry, Multidisciplinary
Vladimir Motornov, Petr Beier
Summary: An efficient one-pot method has been developed for the synthesis of 2-fluoroalkyloxazoles. This method offers a mild and high-yielding approach to prepare structurally diverse fluoroalkylated oxazoles from readily available starting reagents. Furthermore, an alternative direct method using acetonitrile as the solvent has been described for the synthesis of fluoroalkylated oxazoles from electron-rich NH-triazoles.
NEW JOURNAL OF CHEMISTRY
(2022)
