- Synthesis and antifungal activities of pyridine bioisosteres of a bismuth heterocycle derived from diphenyl sulfone
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– Heterocyclic iodobismuthanes 7–9 [IBi(C6H4-2-SO2C5H3N-1′-)] derived from phenyl pyridinyl sulfones were synthesized. Their antifungal activities against the yeast Saccharomyces cerevisiae were compared with those of halobismuthanes [XBi(RC6H3-2-SO2C6H4-1′-)] (1: X=Cl; 2: X=I, R=H) derived from diphenyl sulfone derivatives to determine how the bioisosteric replacement of the benzene ring in 2 with the pyridine ring in 7–9 affects their activities. The antifungal activities of 7–9 were higher or comparable to those of 1 and 2. The DFT calculations suggested that the generation of the antifungal activity of the bismuthanes was well understood by the nucleophilic addition of methanethiolate anion as a model biomolecule at the bismuth atom to give an intermediate ate complex.
- Hafizur Rahman,Murafuji, Toshihiro,Yamashita, Kazuki,Narita, Masahiro,Miyakawa, Isamu,Mikata, Yuji,Ishiguro, Katsuya,Kamijo, Shin
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Read Online
- A Copper(I)-Catalyzed Sulfonylative Hiyama Cross-Coupling
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An air-tolerant Cu-catalyzed sulfonylative Hiyama cross-coupling reaction enabling the formation of diaryl sulfones is described. Starting from aryl silanes, DABSO and aryliodides, the reaction tolerates a large variety of polar functional groups (amines, ketones, esters, aldehydes). Control experiments coupled with DFT calculations shed light on the mechanism, characterized by the formation of a Cu(I)-sulfinate intermediate via fast insertion of a SO2 molecule.
- Adenot, Aurélien,Anthore-Dalion, Lucile,Nicolas, Emmanuel,Berthet, Jean-Claude,Thuéry, Pierre,Cantat, Thibault
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supporting information
p. 18047 - 18053
(2021/11/16)
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- Method for synthesizing sulfone compounds under photocatalysis condition
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The invention belongs to the technical field of compound preparation, and particularly relates to a method for synthesizing sulfone compounds under a photocatalysis condition. Aromatic hydrazine and sulfinate are used as raw materials, and under the action of alkali and a solvent, a sulfone compound is generated through reaction under the condition of air or oxygen under the illumination of visible light. According to the method disclosed by the invention, aryl hydrazine is used as an arylation reagent, polyacid salt is used as a catalyst or an organic photosensitizer is used as a catalyst, and the sulfones compound can be efficiently synthesized by coupling with sulfinate under the condition of room temperature through visible light irradiation. The method has good substrate universalityand relatively mild reaction conditions, is not only a substitute for synthesizing sulfone compounds by coupling from simple substrates reported at present, but also broadens the new application of the polyacid salt in the field of photocatalysis.
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Paragraph 0184-0188
(2021/03/31)
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- Metal-Free Aminomethylation of Aromatic Sulfones Promoted by Eosin Y
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A metal-free α-aminomethylation of heteroaryls promoted by eosin Y under green light irradiation is reported. A large variety of α-trimethylsilylamines as precursor of α-aminomethyl radical species were engaged to functionalize sulfonyl-heteroaryls following a Homolytic Aromatic Substitution (HAS) pathway. This method has provided a range of α-aminoheteroaryl compounds including a functionalized natural product. The mechanism of this late-stage functionalization of aryls was investigated and suggests the formation of a sulfonyl radical intermediate over a reductive quenching cycle.
- Thierry, Thibault,Pfund, Emmanuel,Lequeux, Thierry
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supporting information
p. 14826 - 14830
(2021/10/01)
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- Sulfoxide and Sulfone Synthesis via Electrochemical Oxidation of Sulfides
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The oxidation of diaryl sulfides and aryl alkyl sulfides to the corresponding sulfoxides and sulfones under electrochemical conditions is reported. Sulfoxides are selectively obtained in good yield under a constant current of 5 mA for 10 h in DMF, while sulfones are formed as the major product under a constant current of 10 or 20 mA for 10 h in MeOH. The oxygen of both the sulfoxide and sulfone function is derived from water.
- Lee, Sunwoo,Park, Jin Kyu
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p. 13790 - 13799
(2021/10/12)
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- A [...] or heterocyclic sulfonamide compound preparation method (by machine translation)
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The invention discloses a [...] or heterocyclic sulfonamide compounds of the preparation method, the [...] compound has the formula (I) of the structure shown, the heterocyclic and tissue compound has the formula (II) is shown in the structure, in an organic solvent under the condition of a portion of the inert gas, iodo aromatic ring compound and sodium hydrosulfite under heating conditions in the free radical coupling reaction to obtain the aromatic ring sulfinyl sodium intermediate, with the [...], or iodo alkane, or bromo alkane, or diaryl Iodized salt, or [...] reaction, obtained by the formula (I) has the structure shown as the [...], or formula (II) has the structure shown in the heterocyclic sulfonamide compounds. The method of the invention is simple and efficient, less side reaction, the product has high purity, facilitates separation of the purification, can be suitable for the preparation of a larger scale, with very good application prospect. (by machine translation)
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Paragraph 0084; 0085; 0086; 0087; 0088
(2019/01/21)
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- Method for preparing heterocyclic sulfone or heterocyclic sulfamide compound
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The invention belongs to the technical field of organic synthesis. The invention provides a method for preparing a heterocyclic sulfone or heterocyclic sulfamide compound. The method comprises the following steps: firstly, in a protection atmosphere, under the condition of visible light radiation, carrying out a free radical coupling reaction on an iodo-heteroaromatic compound, thiourea dioxide and sodium hydroxide so as to obtain aromatic heterocyclic sodium sulfinate, wherein a catalyst used in the free radical coupling reaction is fluorescein; and secondly, maintaining a protection atmosphere, carrying out an alkylation reaction or an amidation reaction on the aromatic heterocyclic sodium sulfinate and a group donor compound, thereby obtaining heterocyclic sulfone or heterocyclic sulfamide, wherein the group donor compound is a halogen compound, diaryl or an amino organic matter. The heterocyclic sulfone or the heterocyclic sulfamide can be prepared by only two steps of reactions byusing the method provided by the invention, and in addition, no strong corrosive substance is used, and the method is small in byproduct amount and high in yield.
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Paragraph 0126-0133
(2019/04/04)
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- Ultrasonic-assisted green synthetic method for 2-sulfonyl pyridine derivatives
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The invention discloses an ultrasonic-assisted green synthetic method for 2-sulfonyl pyridine derivatives. The 2-sulfonyl pyridine derivatives are synthesized from 2-halogenated pyridine compounds, sulfonyl chloride compounds and sulfite by one-pot reaction in an aqueous solution under the ultrasonic-assisted action. The raw materials are easily available, the reaction conditions are simple, mild,green and energy-saving, the reaction selectivity and yield are high, and compatibility of substrate functional groups is excellent; particularly, the 2-sulfonyl pyridine derivatives can be obtainedby filtering and direct separation, production cost is reduced, the problem of environmental pollution of the traditional method is solved, and the method has higher application value.
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Paragraph 0085; 0086
(2019/01/16)
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- Convenient and Inexpensive Route to Sulfonylated Pyridines via S N Ar Reaction of Electron-Rich Pyridines by Iron Catalysis
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Sulfonylated pyridines were synthesized in moderate to excellent yields, with a wide scope of substituted pyridines and sulfinate salts as starting materials, by an iron-catalyzed S N Ar reaction. This new methodology exhibits advantages for the synthesis of these useful substrates, such as the use of a readily available, inexpensive catalyst, prevention of the disproportionation of the sulfinate salts, and, more importantly, providing access to electron-rich pyridine substrates.
- Chen, Fei,Chacón-Huete, Franklin,El-Husseini, Hassan,Forgione, Pat
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p. 1914 - 1920
(2018/02/28)
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- Palladium-catalyzed heteroaryl thioethers synthesis overcoming palladium dithiolate resting states inertness: Practical road to sulfones and NH-sulfoximines
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We provide efficient synthetic access to heteroaryl sulfones in two-steps using a simple palladium–1,1′-bis[(diphenyl)phosphanyl]ferrocene catalyst to form in high yields variously functionalized heteroaromatic thioethers. Pyridinyl-containing substrates can be subsequently selectively oxidized into sulfones and NH-sulfoximines by using very mild oxidation conditions with a high functional group tolerance. In the palladium-catalyzed C–S coupling of heteroaromatic thiols, reactivity limitation is attached with electron-deficient thiols. We show that this limitation can be resolved by the successful use of 2-bromoheteroarenes in the C–S coupling. We established herein that this choice of heteroaryl electrophilic reagent in palladium-catalyzed C–S bond formation allows overcoming palladium dithiolate out-of-cycle resting state inertness. This was illustrated in the stoichiometric reactivity study of the palladium dithiolate formed from 4-trifluoromethylbenzen-1-thiol –isolated and characterized by multinuclear NMR and XRD– with both 2-chloropyridine and 2-bromopyridine.
- Guilbaud, Johan,Labonde, Marine,Selmi, Awatef,Kammoun, Majed,Cattey, Hélène,Pirio, Nadine,Roger, Julien,Hierso, Jean-Cyrille
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- Post-synthetically modified SBA-15 with NH2-coordinately immobilized iron-oxine: SBA-15/NH2-FeQ3 as a Fenton-like hybrid catalyst for the selective oxidation of organic sulfides
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A new modified SBA-15 meso-material with NH2-coordinately immobilized "iron-oxine" was fabricated by stepwise covalent grafting of -NH2 and then NH2-coordinate immobilization of tris(8-quinolinolato)iron onto the channels of SBA-15. The structural properties and chemical nature of SBA-15/NH2-FeQ3 were characterized by FTIR, scanning electron microscopy (SEM), SEM-EDX/mapping, transmission electron microscopy (TEM), low angle X-ray diffraction (L-XRD), thermal gravimetric analysis (TGA), N2-adsorption-desorption isotherms (BET) and atomic absorption spectroscopy (AAS). A Fenton-like green and eco-friendly procedure for the catalytic oxidation of aromatic organic sulfides to sulfones using H2O2 was investigated for the synthesised Fe/SBA-15 catalyst. This porous catalyst was found to be reusable for ten runs without appreciable change in the activity, or the composition of the catalyst.
- Golchin Hosseini, Habib,Rostamnia, Sadegh
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p. 619 - 627
(2017/12/28)
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- Deep Eutectic Solvents as Reaction Media for the Palladium-Catalysed C?S Bond Formation: Scope and Mechanistic Studies
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A unique jigsaw catalytic system based on deep eutectic solvents and palladium nanoparticles where C?S bonds are formed from aryl boronic acids and sodium metabisulfite, is introduced. The functionalization step is compatible with a broad spectrum of reagents such as nucleophiles, electrophiles or radical scavengers. This versatile approach allows the formation of different types of products in an environmentally friendly medium by selecting the components of the reaction, which engage one with another as pieces in a jigsaw. This simple procedure avoids the use of toxic volatile organic solvents allowing the formation of complex molecules in a one-pot reaction under mild conditions. Despite the fact that only 1 mol % of metal loading is used, the recyclability of the catalytic system is possible. Kinetic experiments were performed and the reaction order for all reagents, catalyst and ligand was determined. The obtained results were compared to palladium nanocrystals of different known shapes in order to shed some light on the properties of the catalyst.
- Marset, Xavier,Guillena, Gabriela,Ramón, Diego J.
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supporting information
p. 10522 - 10526
(2017/08/10)
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- Access to N-cyanosulfoximines by transition metal-free iminations of sulfoxides
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A transition metal-free synthesis of N-cyanosulfoximines from sulfoxides using N-chlorosuccinimide (NCS) as oxidising agent and cyanamide as nucleophilic amine source is reported. The products are obtained in moderate to excellent yields. The protocol enables an easy access to N-cyanosulfoximines from readily available starting materials under inversion of configuration at a preexisting stereogenic center.
- Dannenberg,Fritze,Krauskopf,Bolm
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p. 1086 - 1090
(2017/02/10)
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- In Situ Generated HypoIodite Activator for the C2 Sulfonylation of Heteroaromatic N-oxides
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A mild approach for direct C2 sulfonylation of heteroaromatic N-oxides with sulfonyl hydrazides affording 2-sulfonyl quinolines/pyridines has been developed. A variety of heteroaromatic N-oxides and sulfonyl hydrazides participate effectively in this transformation which uses hypoiodites (generated in situ from NaI and TBHP) as a means of substrate activators. In this reaction, the N-oxide plays a dual role, acting as a traceless directing group as well as a source of oxygen atom.
- Su, Yuan,Zhou, Xuejun,He, Chunlian,Zhang, Wei,Ling, Xiao,Xiao, Xia
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p. 4981 - 4987
(2016/07/06)
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- H-phosphonate-mediated sulfonylation of heteroaromatic N-oxides: a mild and metal-free one-pot synthesis of 2-sulfonyl quinolines/pyridines
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A smart H-phosphonate-mediated synthetic strategy for the sulfonylation of heteroaromatic N-oxides has been developed, by which a large variety of 2-sulfonyl quinolines/pyridines were synthesized starting from easily available sulfonyl chlorides, diisopropyl H-phosphonate and pyridine/quinoline N-oxides in one pot under metal-free conditions at room temperature.
- Sun, Kai,Chen, Xiao-Lan,Li, Xu,Qu, Ling-Bo,Bi, Wen-Zhu,Chen, Xi,Ma, Hui-Li,Zhang, Song-Tao,Han, Bo-Wen,Zhao, Yu-Fen,Li, Chao-Jun
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supporting information
p. 12111 - 12114
(2015/07/28)
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- NOVEL CHIRAL NITROGEN-PHOSPHORUS LIGANDS AND THEIR USE FOR ASYMMETRIC HYDROGENATION OF ALKENES
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The invention relates to a series of novel chiral nitrogen-phosphorus ligands of formulae (Ia) and (Ib): wherein R1-R3 and X are as defined herein. The invention also relates to chiral metal complexes prepared with these chiral nitrogen-phosphorus ligands. The chiral metal complexes are useful as catalysts for carrying out asymmetric hydrogenation.
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Page/Page column 19; 20
(2015/02/02)
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- Synthesis of pyridyl-dihydrobenzooxaphosphole ligands and their application in asymmetric hydrogenation of unfunctionalized alkenes
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Synthesis of the electron-rich 2-substituted-6-(phenylsulfonyl)pyridines is presented. A series of air-stable, tunable, P-chiral pyridyl- dihydrobenzooxaphosphole ligands were designed and synthesized by a diastereoselective SNAr substitution of the corresponding sulfonyl pyridines. The ligands were successfully applied in the Ir-catalyzed asymmetric hydrogenation of unfunctionalized alkenes with good enantioselectivities.
- Qu, Bo,Samankumara, Lalith P.,Savoie, Jolaine,Fandrick, Daniel R.,Haddad, Nizar,Wei, Xudong,Ma, Shengli,Lee, Heewon,Rodriguez, Sonia,Busacca, Carl A.,Yee, Nathan K.,Song, Jinhua J.,Senanayake, Chris H.
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p. 993 - 1000
(2014/03/21)
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- Metal-free synthesis of diaryl sulfones from arylsulfinic acid salts and diaryliodonium salts
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An efficient, high-yielding, and transition-metal-free synthesis of diaryl sulfones from arylsulfinic acid salts and diaryliodonium salts has been developed. The mild reaction conditions tolerate a range of functional groups, and unsymmetrical diaryliodonium salts show high chemoselectivity.
- Umierski, Natalie,Manolikakes, Georg
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supporting information
p. 188 - 191
(2013/03/28)
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- INDENOPYRIDINE DERIVATIVES
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Disclosed is a compound of formula I and salts thereof. Also disclosed are methods of making the compound of formula (I) and the use of the compound as an intermediate for making pharmaceutically active compounds such as 11- -hydroxysteroid hydrogenase type 1 (11- β-HSD1) inhibitors.
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Page/Page column 13
(2013/03/26)
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- A mild and efficient synthesis of aryl sulfones from aryl chlorides and sulfinic acid salts using microwave heating
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The CuCl-catalyzed coupling of aryl chlorides and sulfinic acid salts provides a simple and extremely efficient route to unsymmetrical aryl sulfones in high to excellent yields under microwave irradiation within 3-30 minutes. Georg Thieme Verlag Stuttgart · New York.
- Yuan, Yan-Qin,Guo, Sheng-Rong
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supporting information; experimental part
p. 2750 - 2756
(2011/12/04)
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- 2-pyridyl sulfoxide: A versatile and removable directing group for the PdII-catalyzed direct C-H olefination of arenes
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Removable and versatile: The 2-pyridylsulfinyl group has proved to be an efficient directing group in the PdII-catalyzed aryl ortho C-H olefination. This catalyst system enables the sequential double olefination to give asymmetrically di-ortho-functionalized arenes. The sulfinyl directing group can be easily cleaved, providing access to 1,3-disubstituted arenes, or transformed into a thiol group.
- Garcia-Rubia, Alfonso,Fernandez-Ibanez, M. Ungeles,Gomez Arrayas, Ramon,Carretero, Juan Carlos
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p. 3567 - 3570
(2011/05/12)
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- NOVEL INTERMEDIATE AND PROCESS USEFUL IN THE PREPARATION OF {2-[1-(3,5-BIS-TRIFLUOROMETHYL-BENZYL)-5-PYRIDIN-4-YL-1H-[1,2,3]TRIAZOL-4-YL]-PYRIDIN-3-YL}-(2-CHLOROPHENYL)-METHANONE
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The present invention relates to novel compounds, (2-chlorophenyl)-[2-(2-hydroxy-2-pyridin-4-yl-vinyl)pyridin-3-yl]methanone benzoate, and (2-chlorophenyl)-[2-(2-hydroxy-2-pyridin-4-yl-vinyl)pyridin-3-yl]methanone toluate, which are useful intermediates for the preparation of the compound of Formula I: (I) The present invention further relates to novel processes for preparing a crystalline compound, which is {2-[1-(3,5-bis-trifluoromethyl-benzyl)-5-pyridin-4-yl-1H-[1,2,3]triazol-4-yl]-pyridin-3-yl}-(2-chlorophenyl)-methanone, Form IV.
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Page/Page column 8
(2008/12/07)
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- Green chemical synthesis of 2-benzenesulfonyl-pyridine and related derivatives
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A practical synthesis of 2-benzenesulfonylpyridine, 1, is described which is a key starting material for the manufacture of an investigational new drug candidate at Eli Lilly and Company. An optimized green chemical process was developed which features a novel tandem SNAr/oxidation under mild conditions to produce the target sulfone, 1, in 86% yield and>99% purity. In addition, this novel, environmentally friendly methodology was found to be general for the synthesis of substituted aromatic pyridyl sulfides and sulfones.
- Trankle, William G.,Kopach, Michael E.
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p. 913 - 917
(2012/12/30)
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- Method for producing 2-sulfonylpyridine derivatives and method for producing 2-{[(2-pyridyl)methyl]thio}-1H-benzimidazole derivatives
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2-Sulfonylpyridine derivatives can be industrially produced efficiently by reacting a sulfonyl cyanide derivative with an α, β-unsaturated carbonyl compound and a 2-{[(2-pyridyl)methyl]thio}-1H-benzimidazole skeleton can be formed in one step in a good yield by reacting this type of the 2-sulfonylpyridine derivative with a 2-methylthio-1H-benzimidazole derivative in the presence of an organolithium compound.
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