- Nickel-Catalyzed Negishi-Type Arylation of Trialkylsulfonium Salts
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Negishi-type arylation of trialkylsulfonium salts with arylzinc reagents has been accomplished under nickel catalysis. The use of cyclohexanethiol as an additional ligand was found to be particularly important to promote C-S cleavage. The present reaction accommodates one-pot arylation of dialkyl sulfides by combining with S -methylation with MeOTf. Mechanistic experiments suggest that C-S cleavage would proceed via single-electron transfer (SET) to generate the most stable carbon-centered radical and that the thiolate ligand would promote the C-S cleavage and radical recombination step.
- Minami, Hiroko,Nogi, Keisuke,Yorimitsu, Hideki
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p. 1542 - 1546
(2021/09/06)
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- Catalytic dehydrogenation of amines to imines and the in-situ reduction of sulfoxides into sulfides
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The catalytic acceptorless dehydrogenation of primary amines into imines and H2 represents one of the most important organic transformations, and the in-situ utilization of the generated H2 for chemical reduction reactions has never
- Li, Bo,Liu, Bing,Liu, Xixi,Wang, Wei,Wang, Yanxin,Xiang, Nian,Zhang, Zehui
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- B2cat2-Mediated Reduction of Sulfoxides to Sulfides
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An efficient and operationally simple method for the reduction of sulfoxides to sulfides has been developed using bis(catecholato)diboron (B2cat2) as a reducing agent. The present method accommodates various functional groups which are generally prone to reduction: halides, alkynes, carbonyls, nitriles, and heterocycles are totally intact, and only sulfoxide moieties undergo reduction chemoselectively. Moreover, the remaining diboron and the resulting boron-containing wastes are readily removable, the practicality of this protocol being thus demonstrated.
- Takahashi, Fumiya,Nogi, Keisuke,Yorimitsu, Hideki
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supporting information
p. 3009 - 3012
(2020/03/25)
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- Nickel phosphide nanoalloy catalyst for the selective deoxygenation of sulfoxides to sulfides under ambient H2pressure
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Exploring novel catalysis by less common, metal-non-metal nanoalloys is of great interest in organic synthesis. We herein report a titanium-dioxide-supported nickel phosphide nanoalloy (nano-Ni2P/TiO2) that exhibits high catalytic activity for the deoxygenation of sulfoxides. nano-Ni2P/TiO2 deoxygenated various sulfoxides to sulfides under 1 bar of H2, representing the first non-noble metal catalyst for sulfoxide deoxygenation under ambient H2 pressure. Spectroscopic analyses revealed that this high activity is due to cooperative catalysis by nano-Ni2P and TiO2. This journal is
- Fujita, Shu,Mitsudome, Takato,Mizugaki, Tomoo,Yamaguchi, Sho,Yamasaki, Jun,Yamazoe, Seiji
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supporting information
p. 8827 - 8833
(2020/11/23)
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- A Manganese N-Heterocyclic Carbene Catalyst for Reduction of Sulfoxides with Silanes
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The first reduction of sulfoxides catalysed by a well-defined manganese complex is described. A variety of sulfoxides are reduced to the corresponding sulfides in high yields using phenylsilane, diphenylsilane, and the economically feasible 1,1,3,3-tetramethyldisiloxane (TMDS) as reducing agents in the presence of a Mn-NHC complex. The reaction is performed under air and without the need of any additive. The involvement of radicals in the catalytic reaction is probed by spin-trap experiments.
- Sousa, Sara C. A.,Carrasco, Carlos J.,Pinto, Mara F.,Royo, Beatriz
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p. 3839 - 3843
(2019/06/24)
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- Aminopyridine-Borane Complexes as Hydrogen Atom Donor Reagents: Reaction Mechanism and Substrate Selectivity
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Lewis base-borane complexes are shown to be potent hydrogen atom donors in radical chain reduction reactions. Results obtained in 1H, 11B, and 13C NMR measurements and kinetic experiments support a complex reaction mechanism involving the parent borane as well as its initial reaction products as active hydrogen atom donors. Efficient reduction reactions of iodides, bromides, and xanthates in apolar solvents rely on initiator systems generating oxygen-centered radicals under thermal conditions and pyridine-borane complexes carrying solubilizing substituents. In contrast to tin hydride reagents, the pyridine-boranes reduce xanthates faster than the corresponding iodides.
- Barth, Florian,Achrainer, Florian,Pütz, Alexander M.,Zipse, Hendrik
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supporting information
p. 13455 - 13464
(2017/10/05)
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- Unprecedented synthesis of iron-NHC complexes by C-H activation of imidazolium salts. Mild catalysts for reduction of sulfoxides
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A direct synthesis of bidentate cyclopentadienyl-functionalised NHC-iron(ii) complexes by using imidazolium salts and commercially available Fe3(CO)12 is developed. These well-defined iron-NHC complexes efficiently catalyse the reduction of sulfoxides under mild conditions. Radical scavenging experiments indicate the presence of free radicals in the catalytic reaction. The Royal Society of Chemistry 2012.
- Cardoso, Joao M.S.,Royo, Beatriz
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scheme or table
p. 4944 - 4946
(2012/06/01)
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- Processes for the synthesis of O-desmethylvenlafaxine
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The present invention describes processes for the preparation of O-desmethylvenlafaxine and tridesmethylvenlafaxine, which may be used as an intermediate in preparing O-desmethylvenlafaxine.
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Page/Page column 5
(2008/12/06)
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- Approaching ambient temperatures in 1,2-DCE to deliver efficient intermolecular D?tz benzannulation processes
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Conditions have been developed that enable intermolecular D?tz benzannulations to be carried out under extremely mild conditions, using 1,2-DCE as the reaction solvent and without the requirement for any additional reaction promoters. The new protocols, at temperatures close to ambient, have been applied successfully to a range of internal and terminal alkynes with a series of aryl and alkenyl carbene complexes, resulting in good to high yields of the benzannulation products. The developed conditions did, however, return lower benzannulation yields when utilised with the traditionally more troublesome 2-furyl carbene complex. It was found that increased reaction temperatures in 1,2-DCE did deliver high yields for the processes with this heteroaryl species.
- Irvine, Stephanie,Kerr, William J.,McPherson, Allan R.,Pearson, Colin M.
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p. 926 - 935
(2008/09/16)
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- The syntheses of sulfides by deoxygenation of sulfoxides using Woollins' reagent
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Woollins' reagent (WR) acts as a deoxygenation reagent for a wide range of sulfoxides affording the corresponding sulfides in good to excellent yields (up to 99% isolated yield) under mild conditions.
- Hua, Guoxiong,Woollins, J. Derek
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p. 3677 - 3679
(2008/02/03)
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- A mild and highly convenient chemoselective alkylation of thiols using Cs2CO3-TBAI
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A mild and improved method for the synthesis of thioethers has been developed. In the presence of cesium carbonate, tetrabutylammonium iodide, and DMF, various alkyl and aryl thiols underwent S-alkylation to afford structurally diverse sulfides in high yield. Unprotected mercaptoalcohols and thioamines reacted chemoselectively at the sulfur moiety exclusively. An example of a one-pot, solid-phase synthesis of a thioether is also described.
- Salvatore, Ralph Nicholas,Smith, Robert A.,Nischwitz, Adam K.,Gavin, Terrence
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p. 8931 - 8935
(2007/10/03)
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- Development of Odorless Thiols and Sulfides and Their Applications to Organic Synthesis
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Development of new odorless thiols (dodecanethiol, 4-n- heptylphenylmethanethiol, 4-trimethylsilylphenylmethanethiol, 4-trimethylsilylbenzenethiol) and an odorless sulfide (1-methylsulfanyldodecane) and their applications to dealkylation, Michael addition, Swern oxidation, and Corey-Kim oxidation are described.
- Nishide, Kiyoharu,Ohsugi, Shin-Ichi,Miyamoto, Tetsuo,Kumar, Kamal,Node, Manabu
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p. 189 - 200
(2007/10/03)
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- New odorless method for the Corey-Kim and Swern oxidations utilizing dodecyl methyl sulfide (Dod-S-Me)
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Development of the odorless dodecyl methyl sulfide (Dod-S-Me, 1) as an alternative for dimethyl sulfide (DMS) and new odorless methods for the Corey-Kim and Swern oxidations are described. These reactions have been developed with a view toward green chemistry, utilizing Dod-S-Me (1) and common solvents instead of dichloromethane.
- Ohsugi, Shin-Ichi,Nishide, Kiyoharu,Oono, Keiji,Okuyama, Kazunori,Fudesaka, Masato,Kodama, Sumiaki,Node, Manabu
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p. 8393 - 8398
(2007/10/03)
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- Ultrasound-promoted deoxygenation of sulphoxides by samarium - NH4Cl
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Several aromatic and aliphatic sulphoxides are selectively deoxygenated to the corresponding thioethers in high to quantitative yields by samarium metal in methanolic ammonium chloride under sonication. Other functional groups such as halides, esters, ethers, nitriles, olefins and ketones are unaffected under the present reaction conditions.
- Yadav,Subba Reddy,Srinivas,Srihari
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p. 854 - 856
(2007/10/03)
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- Synthetic Application of Lithiated Tris(methylthio)methane: Preparation of Aliphatic Methyl Thiolcarboxylates from the Corresponding Halides. Convenient Synthesis of Tris(methylthio)methane
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A thorough study directed towards the synthesis of methyl thiolcarboxylates was made on the basis of the following steps: (i) conversion of alkyl halides into the corresponding trimethyl trithioorthocarboxylates by using tris(methylthio)methyllithium in THF at -78 degC; (ii) selective hydrolysis of the intermediates to methyl thiolcarboxylates by using 35percent aq.HBF4 in DMSO or, in some cases, in THF.The overall yields of the two stages are, usually, between 70 and 88percent.By this procedure it is also possible to incorporate 18O in the carbonyl group of thiol esters (ca. 98percent isotopic purity).Furthermore, a new, convenient method for the preparation of tris(methylthio)methane as the precursor of tris(methylthio)methyllithium was developed.
- Barbero, Margherita,Cadamuro, Silvano,Degani, Iacopo,Dughera, Stefano,Fochi, Rita
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p. 2075 - 2080
(2007/10/02)
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- Alkylation Reactions by Means of Alkanols and Carbon Monoxide: An Efficient Synthesis of Thioethers and of Caffeine from Theophylline
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The reaction of sodium or potassium thiolates with alkanols and carbon monoxide provides a versatile route to produce thioethers in excellent yields.By analogy, the potassium salt of theophylline suffers a nearly quantitative conversion to caffeine when heated with methanol under CO pressure.The mechanism of these alkylation reactions is discussed. - Key Words: Nucleophilic alkylation / Thioethers / Caffeine / Carbon monoxide / Alkanols
- Bott, Kaspar
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p. 1955 - 1956
(2007/10/02)
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- Hydrozirconation of oleyl sulphides and oleyl phenylsulphone
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The hydrozirconation of 9-(Z)-octadecenylmethyl-sulphide, 9-(Z)-octadecenyl phenyl sulphide and 9-(Z)-octadecenyl phenyl sulphone have been studied.These compounds underwent substantial elimination of the functional group, yielding after hydrolysis, along with saturated and unsaturated sulphides and sulphones, large amount of octadecane.The saturated analogues (dodecylmethyl-sulphide, octadecyl phenyl sulphide and octadecylphenyl sulphone) were unaffected by the hydrozirconation reagent under similar conditions.
- Karlsson, Susanne,Hallberg, Anders,Gronowitz, Salo
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- The use of aminoiminomethanesulfinic acid (thiourea dioxide) under phase transfer conditions for generating organochalcogenate anions. Synthesis of sulfides, selenides and tellurides
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A procedure is described which allows for the in situ synthesis of arylalkyl, diaryl and dialkylchalcogenides under phase transfer conditions starting from the corresponding diorganodichalcogenides.The dichalcogenides are reduced by aminoiminomethanesulfinic acid (thiourea dioxide) in alkaline medium and catalyzed by a quaternary ammonium salt.The reduction proceeds easily for diaryl disulfides and diaryl diselenides at a sodium hydroxide concentration of 13percent; diaryl ditellurides require a 50percent sodium hydroxide solution to give the aryl tellurolate anion.The dialkyl diselenides and dialkyl ditellurides are more difficult to reduce.The intermediate arylthiolates and arylselenolates are quenched by alkyl and activated aryl halides to give the corresponding sulfides and selenides in high yield (77-97percent).The aryltellurolates react with alkyl halides giving the aryl alkyl tellurides in 81-96percent yield.The procedure could not be successfully used for the synthesis of dialkylselenides and dialkyl tellurides; low yields and mixture of products were formed.
- Comasseto, J. V.,Lang, E. S.,Ferreira, J. Tercio B.,Simonelli, F.,Correira, V. R.
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p. 329 - 340
(2007/10/02)
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