13596-75-3Relevant academic research and scientific papers
Heterofunctional control of regio- and enantioselectivity in rhodium-catalysed hydroboration of allylic systems
Lillo, Vanesa,Fernandez, Elena
, p. 315 - 319 (2006)
Aryl allylic sulfones were reacted with catecholborane (HBcat) in the presence of neutral and cationic Rh complexes modified with bidentate chiral ligands, to produce the branched heteroorganoboronate ester, as the main isomer with moderate enantioselecti
Flow Electrosynthesis of Sulfoxides, Sulfones, and Sulfoximines without Supporting Electrolytes
Amri, Nasser,Wirth, Thomas
, p. 15961 - 15972 (2021/07/20)
An efficient electrochemical flow process for the selective oxidation of sulfides to sulfoxides and sulfones and of sulfoxides toN-cyanosulfoximines has been developed. In total, 69 examples of sulfoxides, sulfones, andN-cyanosulfoximines have been synthesized in good to excellent yields and with high current efficiencies. The synthesis was assisted and facilitated through a supporting electrolyte-free, fully automated electrochemical protocol that highlights the advantages of flow electrolysis.
Hydrofluoromethylation of alkenes with fluoroiodomethane and beyond
Chen, Xuanxiao,Gouverneur, Véronique,Hell, Sandrine M.,Meyer, Claudio F.,Ortalli, Sebastiano,Sap, Jeroen B. I.
, p. 12149 - 12155 (2021/09/28)
A process for the direct hydrofluoromethylation of alkenes is reported for the first time. This straighforward silyl radical-mediated reaction utilises CH2FI as a non-ozone depleting reagent, traditionally used in electrophilic, nucleophilic and carbene-type chemistry, but not as a CH2F radical source. By circumventing the challenges associated with the high reduction potential of CH2FI being closer to CH3I than CF3I, and harnessing instead the favourable bond dissociation energy of the C-I bond, we demonstrate that feedstock electron-deficient alkenes are converted into products resulting from net hydrofluoromethylation with the intervention of (Me3Si)3SiH under blue LED activation. This deceptively simple yet powerful methodology was extended to a range of (halo)methyl radical precursors including ICH2I, ICH2Br, ICH2Cl, and CHBr2F, as well as CH3I itself; this latter reagent therefore enables direct hydromethylation. This versatile chemistry was applied to18F-,13C-, and D-labelled reagents as well as complex biologically relevant alkenes, providing facile access to more than fifty products for applications in medicinal chemistry and positron emission tomography.
Photocatalytic Giese-Type Reaction with Alkylsilicates Bearing C,O-Bidentate Ligands
Morofuji, Tatsuya,Matsui, Yu,Ohno, Misa,Ikarashi, Gun,Kano, Naokazu
supporting information, p. 6713 - 6718 (2021/02/26)
Herein, a photocatalytic Giese-type reaction with alkylsilicates bearing C,O-bidentate ligands as stable alkyl radical precursors has been reported. The alkylsilicates were prepared in one step from organometallic reagents. Not only primary, secondary, and tertiary alkyl radicals, but also elusive methyl radicals, could be generated by using the present reaction system. The generated radicals were trapped by electron-deficient olefins bearing various functional groups to give the desired alkyl adducts. The silicon byproduct can be recovered after the photoreaction. The radical generation process was investigated by theoretical calculations, which provided an insight into the facile generation of methyl radicals from methylsilicate bearing C,O-bidentate ligands.
Photocatalytic Hydromethylation and Hydroalkylation of Olefins Enabled by Titanium Dioxide Mediated Decarboxylation
Zhu, Qilei,Nocera, Daniel G.
supporting information, p. 17913 - 17918 (2020/12/04)
A versatile method for the hydromethylation and hydroalkylation of alkenes at room temperature is achieved by using the photooxidative redox capacity of the valence band of anatase titanium dioxide (TiO2). Mechanistic studies support a radical-based mechanism involving the photoexcitation of TiO2 with 390 nm light in the presence of acetic acid and other carboxylic acids to generate methyl and alkyl radicals, respectively, without the need for stoichiometric base. This protocol is accepting of a broad scope of alkene and carboxylic acids, including challenging ones that produce highly reactive primary alkyl radicals and those containing functional groups that are susceptible to nucleophilic substitution such as alkyl halides. This methodology highlights the utility of using heterogeneous semiconductor photocatalysts such as TiO2 for promoting challenging organic syntheses that rely on highly reactive intermediates.
Transition-Metal-Free Coupling of Alkynes with α-Bromo Carbonyl Compounds: An Efficient Approach towards β,γ-Alkynoates and Allenoates
Liu, Wenbo,Chen, Zhengwang,Li, Lu,Wang, Haining,Li, Chao-Jun
, p. 5888 - 5893 (2016/04/26)
A direct transition-metal-free coupling between alkynes and α-bromo carbonyl compounds has been developed with ultraviolet (UV) light in aqueous media. This method represents a facile approach to synthetically useful β,γ-alkynyl esters and amides stereoselectively from two readily available starting materials. As an example of the synthetic application of the products, the alkynyl esters were readily converted into allenoates. Time for UV! A direct coupling between alkynes and α-bromo compounds has been developed with ultraviolet light in aqueous media (see scheme). This method represents a facile approach to synthetically useful β,γ-alkynyl esters and amides stereoselectively from two readily available starting materials.
The highly selective metal-free oxidation of sulfides, tellurides and phosphines using sodium bromate in the presence of recyclable ionic liquid [bmim]HSO4, at 80°C
Rajeswari,Lumb, Anshika,Khurana, Jitender M.
, p. 442 - 444 (2016/07/21)
The metal-free oxidation of sulfides to sulfones using sodium bromate (NaBrO3) in [bmim]HSO4:H2O (3:1, v/v) at 80°C is reported. Phenylalkyl, phenylbenzyl, diaryl and heteroaryl sulfides were transformed to the corresponding sulfones. Aryl tellurides and phosphines were oxidised to the corresponding telluroxides and phosphine oxides. All the reactions proceeded smoothly and gave high yields in 20-55 min. The ionic liquid [bmim]HSO4 was easily recovered and recycled.
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.
Cellulose as an efficient support for Mn(salen)Cl: Application for catalytic oxidation of sulfides to sulfoxides
Mohammadinezhad, Arezou,Nasseri, Mohammad Ali,Salimi, Mehri
, p. 39870 - 39874 (2014/12/11)
Supported Mn(salen)Cl was prepared by immobilization of a homogeneous Mn(salen)Cl complex onto cellulose and characterized by FT-IR, TGA and atomic absorption spectroscopy. This heterogeneous catalyst is able to effectively catalyze the oxidation of aromatic sulfides in good yield under mild conditions. The catalytic activity of Mn(salen)Cl and [Mn(salen)Cl-cellulose] in this reaction was investigated. The heterogeneous catalyst showed higher catalytic activity with respect to the neat Mn(salen)Cl complex. The key advantages of this process are cost effectiveness of the catalyst, reusability of the catalyst and easy work-up. This journal is
Aqueous sodium hypochlorite mediated chemoselective oxidation of chalcogenides to monoxides and dioxides by microwave exposure
Khurana, Jitender,Nand, Bhaskara
experimental part, p. 906 - 909 (2011/01/08)
A solvent-free, rapid, and highly selective oxidation of sulfides, selenides, and tellurides (chalcogenides) to the corresponding monoxides (sulfoxides, selenoxides, and telluroxides) or the corresponding dioxides (sulfones, selenones, and tellurones) has been developed using aqueous sodium hypochlorite on solid supports by exposure to microwave. Chemoselectivity and quantitative yields have been attained in most cases.
