19719-87-0Relevant articles and documents
Enantioselective 1,4-addition of cyclopropylboronic acid catalyzed by rhodium/chiral diene complexes
Takechi, Ryosuke,Nishimura, Takahiro
, p. 8528 - 8531 (2015)
Rhodium-catalyzed asymmetric addition of cyclopropylboronic acids to electron-deficient alkenes such as alkenylsulfones, enones, enoates, and nitroalkenes proceeded to give high yields of the corresponding 1,4-addition products with high enantioselectivit
Solvent-mediated switching between oxidative addition and addition-oxidation: Access to β-hydroxysulfides and β-arylsulfones by the addition of thiols to olefins in the presence of Oxone
Moorthy, Jarugu Narasimha,Payra, Soumen,Yadav, Navin
, p. 582 - 591 (2022/01/22)
The reaction between aryl olefins and thiols in the presence of Oxone in toluene-water (9:1, v/v) affords β-hydroxy-2-arylethyl aryl sulfides smoothly by the interception of intermediary thiyl radicals with aryl olefins; the former are generated by the ox
Copper-Catalyzed Chloro-Arylsulfonylation of Styrene Derivatives via the Insertion of Sulfur Dioxide
Li, Yue,Shen, Lin,Zhou, Mi,Xiong, Baojian,Zhang, Xuemei,Lian, Zhong
, p. 5880 - 5884 (2021/08/01)
A copper-catalyzed four-component chloro-arylsulfonylation of styrene derivatives with aryldiazonium tetrafluoroborates, lithium chloride, and ex-situ generated sulfur dioxide (from SOgen) is presented. This sulfonylation features good functional group compatibility, mild reaction conditions, excellent regioselectivity, and good yields. The robustness and potential of this method have also been successfully demonstrated by a gram-scale reaction. Based on experimental study, a radical-involved mechanism is proposed for the transformation.
Metal-Free, Multicomponent Anti-Markovnikov Hydroarylsulfonylation and Alkoxyarylsulfonylation of Vinyl Arenes
Das, Pritha,Das, Subhodeep,Varalaxmi, Kasarla,Jana, Ranjan
, p. 575 - 584 (2020/12/09)
A unified strategy for the hydro-arylsulfonylation of vinyl arenes has been developed under catalyst, additive-free conditions at room temperature from the corresponding aryldiazonium salts, DABSO (DABCO ? 2SO2), and thiophenol as hydrogen atom transfer (HAT) reagent. Mechanistically, an incipient arylsulfonyl radical is generated from the corresponding aryl diazonium salts and DABSO which undergoes anti-Markovnikov addition to styrenes followed by hydrogen atom transfer from thiophenol. Interestingly, this multi-component reaction is highly chemoselective suppressing deleterious thiosulfonylation and thiol-ene reactions. Tuning the reaction conditions, a four-component difunctionalization with alkoxy group has been achieved using 1,4-dicyanobenzene as an oxidant. Furthermore, base-promoted elimination to form vinyl sulfone has been also examined. The practicability of this present reaction has been demonstrated by the ex situ generation of sulfur dioxide in an H-type reaction vessel and subsequent hydro- and alkoxyarylsulfonylation in good to moderate yields. The hydroarylsulfonylation reaction is scalable and applied to a metal-free synthesis of the key intermediate for an anti-migraine drug Eletriptan. (Figure presented.).
Multicomponent Reductive Cross-Coupling of an Inorganic Sulfur Dioxide Surrogate: Straightforward Construction of Diversely Functionalized Sulfones
Meng, Yingying,Wang, Ming,Jiang, Xuefeng
supporting information, p. 1346 - 1353 (2019/12/11)
Conventionally, sulfones are prepared by oxidation of sulfides with strong oxidants. Now, a multicomponent reductive cross-coupling involving an inorganic salt (sodium metabisulfite) for the straightforward construction of sulfones is disclosed. Both intramolecular and intermolecular reductive cross-couplings were comprehensively explored, and diverse sulfones were accessible from the corresponding alkyl and aryl halides. Intramolecular cyclic sulfones were systematically obtained from five- to twelve-membered rings. Naturally occurring aliphatic systems, such as steroids, saccharides, and amino acids, were highly compatible with the SO2-insertion reductive cross-coupling. Four clinically applied drug molecules, which include multiple heteroatoms and functional groups with active hydrogens, were successfully prepared via a late-stage SO2 insertion. Mechanistic studies show that alkyl radicals and sulfonyl radicals were both involved as intermediates in this transformation.
Aryl alkyl sulfone compound and reducing coupling method for constructing sulfone compounds
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Paragraph 0177-0181, (2019/12/25)
The invention discloses an aryl alkyl sulfone compound shown as a formula (1) and a synthetic method thereof. The aryl alkyl sulfone compound is prepared by taking an aromatic iodide, an inorganic sulfur reagent and an alkyl bromide as reaction raw materials to carry out reacting in a solvent under action of alkali, a catalyst, a ligand, a reducing agent and an additive. According to the invention, an inorganic sulfur reagent is used as a sulfur source to construct the aryl alkyl sulfone compound in one step under catalysis and reduction conditions, so that the defect in synthesizing the arylalkyl sulfone compound by conventional oxidation of thioether is avoided. The aryl alkyl sulfone compound developed by the invention can be used for synthesizing aryl alkyl sulfone medicines.
Copper-catalyzed regioselective synthesis of (E)-β-fluorovinyl sulfones
Román, Raquel,Barrio, Pablo,Mateu, Natalia,Sedgwick, Daniel M.,Fustero, Santos
, (2019/05/02)
Organofluorine compounds are finding increasing application in a variety of fields such as pharmaceutical, agrochemical, and material sciences. However, given the scarcity of fluorine-containing natural products, advancement in this area depends almost entirely on the development of new synthetic methodologies. In this article, we present the synthesis of a series of previously undescribed (E)-β-fluorovinyl sulfones via a simple copper-catalyzed addition of hydrogen fluoride to alkynyl sulfone starting materials in varying yields and E/Z selectivities. The hydrogenation of these products was also explored and compared with the hydrogenation of the related Z isomers. These new products may find interesting applications, given the versatility of vinyl sulfones in chemical synthesis and the unique properties of vinyl fluorides in biological settings.
A metal-free and regioselective approach to (Z)-β-fluorovinyl sulfones and their chemoselective hydrogenation to β-fluoroalkyl sulfones
Sedgwick, Daniel M.,Román, Raquel,Barrio, Pablo,Morales, Cristina,Fustero, Santos
, p. 108 - 116 (2018/01/01)
A highly regioselective, metal-free hydrofluorination reaction of alkynyl sulfones was developed using TBAF—one of the cheapest and most commonly available fluoride sources. In addition, the reactivity of the resulting β-fluorovinyl sulfones was studied, focusing on their selective hydrogenation reaction. Both β-fluorovinyl sulfones and their hydrogenation products β-fluoroalkyl sulfones may find applications in medicinal and agrochemical sciences.
Palladium-Catalyzed Synthesis of (Hetero)Aryl Alkyl Sulfones from (Hetero)Aryl Boronic Acids, Unactivated Alkyl Halides, and Potassium Metabisulfite
Shavnya, Andre,Hesp, Kevin D.,Mascitti, Vincent,Smith, Aaron C.
supporting information, p. 13571 - 13575 (2015/11/16)
A palladium-catalyzed one-step synthesis of (hetero)aryl alkyl sulfones from (hetero)arylboronic acids, potassium metabisulfite, and unactivated or activated alkylhalides is described. This transformation is of broad scope, occurs under mild conditions, and employs readily available reactants. A stoichiometric experiment has led to the isolation of a catalytically active dimeric palladium sulfinate complex, which was characterized by X-ray diffraction analysis.
Synthesis of biaryls via intramolecular free radical ipso-substitution reactions
Ujjainwalla, Feroze,Da Mata, Maria Lucília E.N.,Pennell, Andrew M.K.,Escolano, Carmen,Motherwell, William B.,Vázquez, Santiago
, p. 6701 - 6719 (2015/08/24)
A variety of functionalised biaryls and heterobiaryls are prepared by intramolecular free radical [1,5]-ipso-substitution using sulfonamide and sulfonate derived tethering chains. The overall efficiency of the process is determined by appropriately positioned substituents on the aromatic acceptor ring. The extension of the process to benzylic sulfonates and their corresponding N-methylsulfonamide alternatives as substrates in potential [1,6]-ipso-substitution reactions leads mainly to the alternative [1,7] addition products.
