- Electrochemical Properties and Reactions of Sulfur-Containing Organoboron Compounds
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Electrochemical analyses of 4,4,5,5-tetramethyl-2-phenylsulfanylmethyl-[1,3,2]dioxaborolane and tetra-n-butylammonium phenylthiomethyltrifluoroborate were comparatively studied by cyclic voltammetry measurements and we found for the first time the β-effect of organoborate, which was indicated by experimental and theoretical aspects. The organoborate was found to have a much lower oxidation potential compared to the organoborane. Anodic substitution reaction of organoboronate ester and organoborate was successfully carried out in the presence of nucleophiles to afford the selectively substituted products in good yields.
- Tanigawa, Masahiro,Kuriyama, Yu,Inagi, Shinsuke,Fuchigami, Toshio
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- Anodic Dehydrogenative Cyanamidation of Thioethers: Simple and Sustainable Synthesis of N-Cyanosulfilimines
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A novel and very simple to perform electrochemical approach for the synthesis of several N-cyanosulfilimines in good to excellent yields was established. This method provides access to biologically relevant sulfoximines by consecutive oxidation using electro-generated periodate. This route can be easily scaled-up to gram quantities. The S,N coupling is carried out at an inexpensive carbon anode by direct oxidation of sulfide. Therefore, the designed process is atom economic and represents a new “green route” for the synthesis of sulfilimines and sulfoximines.
- Klein, Martin,Waldvogel, Siegfried R.
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supporting information
p. 23197 - 23201
(2021/09/25)
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- Synthesis of dithioacetals and oxathioacetals with chiral auxiliaries
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One-pot synthesis of dithioacetals as well as an efficient method for oxathioacetal is reported. Additionally, some chiral auxiliaries were used to synthesize enantiomerically pure dithioacetals and oxathioacetals.
- Zaidi, Javid H.,Naeem, Fazal,Khan, Khalid M.,Iqbal, Rasfaid,Zia-Ullah
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p. 2641 - 2653
(2007/10/03)
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- Electrooxidative Inter- and Intramolecular Carbon-Carbon Bond Formation Using Organothio Groups as Electroauxiliaries
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The introduction of an organothio group to an α-carbon of ethers results in significant decrease of the oxidation potentials. Anodic oxidation of α-organothioethers gives rise to facile cleavage of the C-S bond and the introduction of carbon nucleophiles on the carbon. Allylsilanes, silyl enol ethers, and trimethylsilyl cyanide serve as effective carbon nucleophiles. The anodic oxidation of the α-organothioethers having a carbon-carbon double bond in an appropriate position using Bu4-NBF4 as the supporting electrolyte leads to the effective cyclization and the introduction of the fluoride to one of the formal olefinic carbon. The present study demonstrates the effectiveness of organothio groups as electroauxiliaries in electrooxidative inter- and intramolecular carbon-carbon bond formation.
- Yoshida, Jun-Ichi,Sugawara, Masanobu,Tatsumi, Masao,Rise, Naoki
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p. 5950 - 5961
(2007/10/03)
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- Spectral and Thermodynamic Characteristics of Complexes of Seleno- and Thioacetals with Iodine
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Seleno- and thioacetal complexes of iodine were studied spectrophotometrically. The spectral and thermodynamic parameters of the complexes are compared with the special features of the electronic and steric structure of the donor molecules and with the characteristics of tetracyanoethylene complexes of the same compounds.
- Kazymova,Nedugov,Pavlova,Chmutova
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- Ketone homologation to produce α-methoxyketones: Application to conduritol synthesis
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The scope of Trost's sulfone homologation procedure for the conversion of ketones into their α-methoxylated higher homologues has been dramatically expanded. The use of zirconium (or hafnium) tetrachloride in the hydroxy sulfone rearrangement step gives g
- Phillipson, Neil,Anson, Michael S.,Montana, John G.,Taylor, Richard J. K.
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p. 2821 - 2829
(2007/10/03)
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- Cross Aldol Products from α-Haloalkoxysilanes and Silyl Enol Ethers
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α-Haloalkoxysilanes have been prepared by cleavage of the C-S bond in O,S-acetals with sulfuryl chloride, and by cleavage of C-Sn bond in α-silyloxystannanes by bromine.The α-haloalkoxysilanes, both after isolation or after preparation in situ react with silyl enol ethers to yield silyl-protected cross aldol products.The reaction is catalyzed by Lewis acids.
- Antonsen, Oeyvind,Benneche, Tore,Gundersen, Lise-Lotte,Undheim, Kjell
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p. 172 - 177
(2007/10/02)
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- Fluoride Ion Promoted Anodic Substitutions of Chalcogeno Compounds. 1. Regioselective Anodic Alkoxylation of Sulfides
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Anodic α-alkoxylation of sulfides was remarkably promoted in the presence of fluoride ions: When Et3N*3HF was used as a supporting electrolyte, simple alkyl phenyl sulfides and sulfides bearing weak electron-withdrawing groups underwent anodic alkoxylatio
- Fuchigami, Toshio,Yano, Hidetoshi,Konno, Akinori
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p. 6731 - 6733
(2007/10/02)
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- Anodic Oxidation of (Trimethylsilyl)methanes with ?-Electron Substituents in the Presence of Nucleophiles
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It was found that oxidation potentials of methanes with ?-electron substituents were decreased by introduction of a trimethylsilyl group.The anodic oxidation of benzyl-, allyl-, aryl(or alkyl)thiomethyl-, and aryloxymethyl-substituted trimethylsilanes smoothly proceeded in the presence of nucleophiles, e.g. alcohols and carboxylic acids, to eliminate the trimethylsilyl groups giving the corresponding alkoxylated and carboxylated products in moderate or high yields without full optimization of electrolytic conditions, while aminomethylsilanes did not undergo such a kind of anodic oxidation.
- Koizumi, Toshio,Fuchigami, Toshio,Nonaka, Tsutomu
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p. 219 - 225
(2007/10/02)
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- Indirect Electrooxidation Mediated by an Ni(III)/(II) Redox Couple with a Cyclam Ligand
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The first example of an Ni(III)-mediated indirect electrolysis was found in the oxidation of silicon compounds using an Ni(III)/(II) redox couple having a macrocyclic polyamine (cyclam) as a ligand.
- Takiguchi, Tsuyoshi,Nonaka, Tsutomu
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p. 1217 - 1218
(2007/10/02)
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- A Novel Synthesis of Phenylthiomethyl (PTM) Ethers and Esters by Anodic Oxidation of Phenyl Trimethylsilylmethyl Sulfide
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It was found that anodic oxidation of phenyl trimethylsilylmethyl sulfide in the presence of alcohols and carboxylic acids afforded various kinds of PTM ethers and esters, respectively, in good to reasonable yields.
- Koizumi, Toshio,Fuchigami, Toshio,Nonaka, Tsutomu
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p. 1095 - 1096
(2007/10/02)
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- lithium and lithium. Convenient Reagents for the Facile Conversion of Aldehydes, Ketones, and 3-Alkoxy Enones into Ketene O,S-Acetal Derivatives
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The title organometalics have been found to react in the 1,2-sense with a variety of carbonyl compounds to provide O,S-acetal and ketene O,S-acetal derivatives in high yield.The β,γ-unsaturated O,S-acetals obtained via the reaction of methoxy(phenylthio)
- Hackett, Steven,Livinghouse, Tom
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p. 879 - 885
(2007/10/02)
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- A Concise Synthetic Route to Polyfunctional γ-Ketoester Derivatives via Methoxy(phenylthio)methyl-lithium
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The α,β-unsaturated O,S-acetals obtained via the reaction of methoxyphenylthiomethyl-lithium with 3-alkoxyenones are readily convertible into structurally diverse γ-ketoesters by way of an efficient alkylation-hydrolysis sequence.
- Hackett, Steven,Livinghouse, Tom
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- A Facile Synthesis of Sulfides Using S-Aryl-isothiuronium Intermediates
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A variety of sulfides were conveniently prepared by a treatment of aryl iodides with thiourea in the presence of nickel(0) catalyst, then with CaO, and finally with a variety of electrophiles such as alkyl, acyl, silyl, aryl, or alkenyl halides.
- Takagi, Kentaro
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p. 1379 - 1380
(2007/10/02)
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- SYNTHESIS OF VINYL ETHERS BY HOMOLOGATION OF ALDEHYDES VIA RADICAL REDUCTIVE ELIMINATION
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Methoxyphenylthiomethyllithium 1 reacts with aldehydes to give adducts which are then transformed into xanthates.These compounds, by reaction with tri-n-butylstannane, afford vinyl ethers in good yields.
- Vatele, Jean-Michel
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p. 5997 - 6000
(2007/10/02)
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- Sulfur Heterocycles. 3. Heterogeneous, Phase-Transfer, and Acid-Catalyzed Potassium Permanganate Oxidation of Sulfides to Sulfones and a Survey of their Carbon-13 Nuclear Magnetic Resonance Spectra
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Although numerous oxidation methods are available for the transformation of sulfides into sulfones, low-molecular-weight, heterocyclic sulfides are often not amenable to this oxidation techniques.The method presented here is a general and economical oxidation using potassium permanganate and various catalysts.Nineteen low-molecular-weight and heterocyclic sulfides were successfully oxidized by variations of this technique, and the results are presented here.In addition, the carbon-13 NMR spectra of these compounds and about two dozen others are reported.General chemical shift trends are reported for selected compounds, and details can be found in the supplementary material.
- Gokel, George W.,Gerdes, Harold M.,Dishong, Dennis M.
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p. 3634 - 3639
(2007/10/02)
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