- Racemic and optically active 1,1′-binaphthyl-2,2′-diyl sulfite: Synthesis, crystal structure, and ring-opening reactions with selected nucleophiles
-
Preparation of the sulfite derived from racemic and (R)-(+)-enantiomer of BINOL is reported. The crystal structure of the optically active, levorotatory sulfite isomer and its ring opening induced by nucleophilic substitution reactions with selected nucleophiles are presented.
- Drabowicz, Jozef,Krasowska, Dorota,Marciniak, Bernard,Rozycka-Sokolowska, Ewa
-
-
Read Online
- Diastereoisomerically pure, (S)-O-1,2-O-isopropyli dene-(5-O-α-d-glucofuranosyl) t-butanesulfinate: Synthesis, crystal structure, absolute configuration and reactivity
-
The reaction of t-butylmagnesium chlorides with diastereomerically pure (R)-1,2-Oisopropylidene-3,5-O-sulfinyl-α-d-glucofuranose (R)-4 was found to be stopped at the stage of the corresponding, diastereoisomerically pure 1,2-O-isopropylidene-(5-O-α-d-glucofuranosyl) t-butanesulfinate (S)-10 for which the crystal structure and the (S)-absolute configuration was determined by X-ray crystallography. Comparison of the absolute configurations of the starting sulfite (R)-4, and t-butanesulfinate (S)-10 (which crystallizes in the orthorhombic system, space group P212121, with the single compound molecule present in the asymmetric unit), clearly indicates that the reaction of nucleophilic substitution at the stereogenic sulfur atom in the sulfite (R)-4 occurs with the full inversion of configuration via the trigonal bipyramidal sulfurane intermediate 4c in which both the entering and leaving groups are located in apical positions.
- B?aszczyk, Jaros?aw,Bujnicki, Bogdan,Chmielewski, Marek,Drabowicz, Józef
-
-
Read Online
- Lithium/Sodium Perchlorate Catalyzed Synthesis of Symmetrical Diaryl Sulfoxides
-
Synthesis of diaryl sulfoxides from aromatics and thionyl chloride catalyzed by LiClO4/NaClO4 at room temperature is described. Mild reaction conditions, simple work-up, inexpensive and easily available catalysts are important and attractive features of this method.
- Bandgar,Makone
-
-
Read Online
- Selective synthesis of sulfoxides and sulfonesviacontrollable oxidation of sulfides withN-fluorobenzenesulfonimide
-
A practical and mild method for the switchable synthesis of sulfoxides or sulfonesviaselective oxidation of sulfides using cheapN-fluorobenzenesulfonimide (NFSI) as the oxidant has been developed. These highly chemoselective transformations were simply achieved by varying the NFSI loading with H2O as the green solvent and oxygen source without any additives. The good functional group tolerance makes the strategy valuable.
- Cao, Zhong-Yan,Li, Xiaolong,Lu, Hao,Wang, Panpan,Wang, Shengqiang,Xu, Xiaobo,Yan, Leyu,Yang, A-Xiu
-
supporting information
p. 8691 - 8695
(2021/10/22)
-
- Electrochemical oxygenation of sulfides with molecular oxygen or water: Switchable preparation of sulfoxides and sulfones
-
A practical and eco-friendly method for the controllable aerobic oxygenation of sulfides by electrochemical catalysis was developed. The switchable preparation of sulfoxides and sulfones was effectively controlled by reaction time, in which both molecular oxygen and water can be used as the oxygen source under catalyst and external oxidant-free conditions. The electrochemical protocol features a broad substrate scope and excellent site selectivity and is successfully applied to the modification of some sulfide-containing pharmaceuticals and their derivatives. This journal is
- Li, Jin-Heng,Li, Yang,Sun, Qing,Xue, Qi,Zhang, Ting-Ting
-
supporting information
p. 10314 - 10318
(2021/12/17)
-
- Synergistic cooperative effect of CF3SO2Na and bis(2-butoxyethyl)ether towards selective oxygenation of sulfides with molecular oxygen under visible-light irradiation
-
A safe, practical and eco-friendly method for the switchable synthesis of sulfoxides and sulfones through visible-light-initiated oxygenation of sulfides at ambient temperature under transition-metal-, additives-free and minimal solvent conditions. The synergistic catalytic efforts between CF3SO2Na and 2-butoxyethyl ether represents the key promoting factor for the reaction. This journal is
- Liu, Kai-Jian,Wang, Zheng,Lu, Ling-Hui,Chen, Jin-Yang,Zeng, Fei,Lin, Ying-Wu,Cao, Zhong,Yu, Xianyong,He, Wei-Min
-
supporting information
p. 496 - 500
(2021/01/28)
-
- Vanadium-catalyzed Selective Oxidation of Sulfides to Sulfoxides and Sulfones with H2O2
-
Abstract: A direct selective approach to the oxidation of sulfides to sulfoxides andsulfones with H2O2 in moderate togood yields is developed. The reaction proceeds in the presence of 2 mol % ofVO(acac)2 at room temperature. All sulfoxides andsulfones were detected by gas chromatography, and the molecular structures of2-methylbenzyl 4-methylphenyl sulfone, 4-methylbenzyl 4-methylphenyl sulfone,2-bromobenzyl 4-methylphenyl sulfone, and 4-tert-butylbenzyl benzyl sulfone were determined by singlecrystal X-ray crystallography.
- Chen, M.,Jia, A.-Q.,Zhang, P.-Z.,Zhang, Q.-F.,Zhou, W.-Y.
-
p. 816 - 824
(2021/06/12)
-
- Palladium-Catalyzed Sulfinylation of Aryl- And Alkenylborons with Sulfinate Esters
-
An efficient, direct sulfinylation of organoborons catalyzed by palladium is disclosed. Treatment of organoborons and sulfinate esters in the presence of a palladium precatalyst provided a broad range of sulfoxides. Various organosulfur compounds having oxidizable functional groups were successfully prepared through the sulfoxide synthesis.
- Hosoya, Takamitsu,Kanemoto, Kazuya,Nakamura, Yu,Suzuki, Minori,Yoshida, Suguru
-
supporting information
p. 3793 - 3797
(2021/05/29)
-
- Synthesis of an anthraquinone-containing polymeric photosensitizer and its application in aerobic photooxidation of thioethers
-
Work on the synthesis of a polymeric photosensitizer and its application in the photooxidation of thioethers is reported herein. Firstly, the polymeric photosensitizer was designed and synthesized by the reaction of anthraquinone-2-carbonyl chloride (AQ-2-COCl) with poly(2-hydroxyethyl methacrylate) (PHEMA). Then, the visible light-induced photooxidation of thioethers under aerobic conditions was investigated. The results revealed that the reaction yielded sulfoxides highly chemoselectively in excellent yields with good substrate tolerance. Importantly, AQ-PHEMA could be easily recovered and reused more than 20 times without significant loss of the catalytic activity.
- Chen, Yang,Ding, Aishun,Hu, Jianhua
-
p. 10661 - 10665
(2020/03/27)
-
- Selective oxidation of (hetero)sulfides with molecular oxygen under clean conditions
-
The development of eco-friendly and switchable catalytic systems for the conversion of a sole raw-material into distinct high-value products is a particularly attractive concept and a daunting synthetic challenge. In the present work, the first example of efficient and selective oxidation of sulfides to sulfones and sulfoxides using molecular oxygen under clean conditions was established.
- Liu, Kai-Jian,Deng, Ji-Hui,Yang, Jie,Gong, Shao-Feng,Lin, Ying-Wu,He, Jun-Yi,Cao, Zhong,He, Wei-Min
-
supporting information
p. 433 - 438
(2020/02/13)
-
- Oxidation of aromatic sulfides with molecular oxygen: Controllable synthesis of sulfoxides or sulfones
-
The recent development of selective oxidation of aromatic sulfides with molecular oxygen was highlighted. The sulfoxides and sulfones could be obtained by simply switching the reaction media, i.e., bis(2-butoxyethyl)ether (BBE) or poly(ethylene glycol)dimethyl ether (PEGDME). The application of the high-boiling-point polyether as an initiator and green media can eliminate the need of large quantities of additives and volatile solvents. This strategy represents an economic and eco-friendly method that could find potential applications.
- Tang, Lili,Du, Kejie,Yu, Bing,He, Liangnian
-
p. 2991 - 2992
(2020/03/24)
-
- Synthesis and nano-Pd catalyzed chemoselective oxidation of symmetrical and unsymmetrical sulfides
-
A highly chemoselective, efficient and nano-Pd catalyzed protocol for the rapid construction of sulfoxides and sulfones via the oxidation of symmetrical and unsymmetrical sulfides using H2O2 as an oxidant has been developed, respectively. The ready availability of starting materials, easy recovery and reutilization of the catalyst, wide substrate scope, and high yields make this protocol an attractive alternative. The process also involves the metal-free and microwave-promoted synthesis of symmetrical diarylsulfides, and FeCl3-mediated preparation of symmetrical diaryldisulfides through the reaction of arenediazonium tetrafluoroborates with Na2S·9H2O as a sulfur source. In addition, unsymmetrical sulfides were generated via the K2CO3-mediated reaction of arenediazonium tetrafluoroborates with symmetrical disulfides.
- Li, Xing,Du, Jia,Zhang, Yongli,Chang, Honghong,Gao, Wenchao,Wei, Wenlong
-
p. 3048 - 3055
(2019/03/21)
-
- Applications of DUT-67 (Zr) in preparation of methylphenyl sulfoxide through photocatalytic oxidation of thioanisole
-
The invention discloses applications of Zr-MOF(DUT-67) in preparation of methylphenyl sulfoxide through photocatalytic oxidation of thioanisole, and belongs to the technical field of photocatalysis, wherein DUT-67 (Zr) is a metal-organic framework material with high thermal stability and high chemical stability. According to the present invention, DUT-67 (Zr) is firstly used as a photocatalyst toperform organic synthesis, such that the applications of the high-stability Zr-based MOF in the field of photocatalysis are further expanded; under all-band and 360 nm wavelength light sources, DUT-67(Zr) has high activity in photocatalytic oxidation of thioanisole, such that the problems of complex reaction process, high toxicity, easy pollution and low efficiency in the traditional preparationprocess can be successfully solved; and the method has characteristics of simple process, environmental protection, high yield, stable and efficient catalysis process and broad potential, and can be used for large-scale actual production.
- -
-
Paragraph 0019; 0020
(2019/09/10)
-
- Preparation method for sulfoxide compound
-
The invention discloses a preparation method for a sulfoxide compound and belongs to the technical field of catalysis. The invention provides a new green and environment-friendly method for efficiently synthesizing the sulfoxide compound. Under the action of catalyst, thiophenol, aryl diazonium compound and oxidizing agent are directly oxidized into the sulfoxide compound under the condition of light radiation, wherein cercosporin is served as the catalyst. According to the method disclosed by the invention, cercosporin is served as the catalyst; catalyzing condition is mild; catalysis can beperformed under room temperature and radiation of visible light; catalytic activity of catalyst is high; the catalyst can high-selectively catalyze synthesis of sulfoxide compound; with a trace amountof catalyst, yield can reach up to above 70%. The preparation method disclosed by the invention has the advantages of simple and easily acquired photocatalyst and substrate raw materials, environmental protection, low cost, large batch production and bright application prospect.
- -
-
Paragraph 0004; 0042; 0043
(2019/04/10)
-
- Catalyst-free visible-light-initiated oxidative coupling of aryldiazo sulfones with thiols leading to unsymmetrical sulfoxides in air
-
A facile and efficient visible-light-driven method has been developed to construct sulfoxides via oxidative coupling of aryldiazo sulfones with thiols using the O2 in air as the oxidant. This reaction could be performed at room temperature under catalyst- and additive-free conditions. The present methodology offers a mild and environmentally benign approach to obtain a library of sulfoxides in good yields with favorable functional group tolerance.
- Liu, Qishun,Wang, Leilei,Yue, Huilan,Li, Jiang-Sheng,Luo, Zidan,Wei, Wei
-
supporting information
p. 1609 - 1613
(2019/04/08)
-
- Method for preparing visible light promoted asymmetric sulfoxide compound
-
The invention belongs to the field of organic synthetic chemistry, particularly relates to a preparation method of an asymmetric sulfoxide compound, and particularly discloses a method for synthesizing the asymmetric sulfoxide compound based on visible light catalysis. A compound shown in the formula I and a compound shown in the formula II are added to a reactor, a mixture of an organic solvent and water is added as a reaction solvent, the reactor is connected to air, under the irradiation of visible light, a reaction at a room temperature is performed for 16-40 hours; and after a detection reaction of a TLC thin layer chromatography plate is completed, pure water is added, then the extraction is performed, extract liquid is combined and dried, the extract liquid is concentrated and purified to obtain a compound shown in the formula III, and the compound is the asymmetric sulfoxide compound. The reaction conditions are mild, energy is clean, a strong oxidant is not needed, the safetyof the reaction is improved, the pollution caused by using a metal reagent is avoided, and the reaction cost is saved.
- -
-
Paragraph 0047; 0048
(2019/06/11)
-
- Transition-Metal-Free Arylations of In-Situ Generated Sulfenates with Diaryliodonium Salts
-
A transition-metal-free arylation of sulfenate anions generated from β-sulfinyl esters with diaryliodonium salts was developed. In this process, a new C-S bond is formed under mild reaction conditions providing a wide range of S,S-diaryl and S-alkyl S-aryl sulfoxides.
- Yu, Hao,Li, Zhen,Bolm, Carsten
-
supporting information
p. 7104 - 7106
(2018/11/23)
-
- One-Pot Sulfoxide Synthesis Exploiting a Sulfinyl-Dication Equivalent Generated from a DABSO/Trimethylsilyl Chloride Sequence
-
A one-pot process for the synthesis of unsymmetrical sulfoxides using organometallic nucleophiles is described. Sulfur dioxide, delivered from the surrogate DABSO (DABCO-bis(sulfur dioxide)), acts as the initial electrophile and combines with the first organometallic reagent to generate a sulfinate intermediate. In situ conversion of the sulfinate to a sulfinate silyl ester, using TMS-Cl (trimethylsilyl chloride), generates a second electrophile, allowing addition of a second organometallic reagent. Organolithium or Grignard reagents can be employed, delivering sulfoxides in good to excellent yields.
- Lenstra, Danny C.,Vedovato, Vincent,Ferrer Flegeau, Emmanuel,Maydom, Jonathan,Willis, Michael C.
-
supporting information
p. 2086 - 2089
(2016/06/01)
-
- Synthesis of sulfur-bridged polycycles via Pd-catalyzed dehydrogenative cyclization
-
A general approach to sulfur-bridged polycycles by palladium-catalyzed double C(sp2)-H bond oxidative cyclization is presented. This protocol afforded diverse sulfur-bridged five-, six-, and seven-membered polycycles in moderate to good yields with a tolerance for a wide variety of functional groups. A sulfide-bridged six-membered pyrene-thienoacene compound was synthesized readily using this method, and excellent performance for photoluminescence quantum yield was observed.
- Wang, Binjie,Liu, Yue,Lin, Cong,Xu, Yiming,Liu, Zhanxiang,Zhang, Yuhong
-
p. 4574 - 4577
(2015/01/08)
-
- Direct S-arylation of unactivated arylsulfoxides using [Pd(IPr*)(cin) Cl]
-
The direct S-arylation of unactivated arylsulfoxides catalyzed by [Pd(IPr*)(cin)Cl] is described. Several arylmethylsulfoxides were coupled to various aryl halides in moderate to good yields (17 examples, 34-85%). Scope, limitations, and reaction mechanis
- Izquierdo, Frédéric,Chartoire, Anthony,Nolan, Steven P.
-
p. 2190 - 2193
(2013/10/22)
-
- Investigations on the Lewis-acids-catalysed electrophilic aromatic substitution reactions of thionyl chloride and selenyl chloride, the substituent effects, and the reaction mechanisms
-
The previously established aluminium-chloride-(AlCl3)-catalysed electrophilic aromatic substitution (EAS) of benzene (PhH) with thionyl chloride (SOCl2) has been extended to toluene (PhCH3), chlorobenzene (PhCl), and phenol (PhOH). -CH3 was found to be mainly a para-director with a minor ortho-directing effect on the EAS reactions giving diaryl sulfoxides (Ar2SO). -Cl was found to be exclusively a para-director for formation of Ar2SO. All the -CH3, -Cl, and -OH groups were shown to be exclusive para-directors for formation of diaryl sulfides (Ar2S) from the EAS reactions. Although the reactions of PhH and PhCH3 with SOCl2 in the presence of AlCl 3 gave the major Ar2SO and minor Ar2S at ambient temperature, the phenol (PhOH) reaction was shown to give only the reduced sulfide (p-HOC6H4)2S with no sulfoxide (p-HOC6H4)2SO formed. The mixed diaryl sulfoxides ArSOAr′ (Ar, Ar′=C6H5, p-CH 3C6H4; C6H5, o-CH 3C6H4; and C6H5, p-ClC6H4) were produced in the AlCl3-catalysed reactions of SOCl2 with molar 1:1 PhH-PhX mixtures (X=CH3 and Cl). Efforts to enhance the yield of S-aryl arenesulfonothioates ArSO 2SAr (Ar=Ph, p-CH3C6H4, and p-ClC6H4) from the AlCl3-catalysed EAS reactions of SOCl2 were made, showing that decreasing the molar ratios of ArH/SOCl2 or lowering the temperature resulted in an increase in the product yield. A detailed mechanism has been proposed to account for the formation of ArSO2SAr. The Lewis-acid-MCl3-(M=Al and Fe)-catalysed EAS reactions of PhH with selenyl chloride (SeOCl2) were demonstrated to give the reduced diphenyl selenide (Ph2Se) and diphenyl diselenide (PhSeSePh) via novel auto-redox processes in selenium of the key EAS intermediates.
- Sun, Xiaoping,Haas, David,McWilliams, Samantha,Smith, Benjamin,Leaptrot, Katrina
-
p. 736 - 744
(2014/01/23)
-
- Desymmetrization of prochiral diaryl sulfoxides by an asymmetric sulfoxide-magnesium exchange
-
The first desymmetrizations of prochiral diaryl sulfoxides 1 by an asymmetric sulfoxide-magnesium exchange reaction are reported. The respective substrate (1), iPr2Mg, and the dilithium salt of (S)-BINOL (which was prepared in situ) provided (S)-configured aryl isopropyl sulfoxides 2 in up to 91 % yield and with up to 91 % ee. (S)-BINOL was re-isolable in 98 % yield. Copyright
- Hampel, Thomas,Ruppenthal, Simon,Saelinger, Daniel,Brueckner, Reinhard
-
supporting information; body text
p. 3136 - 3140
(2012/05/20)
-
- Mild and efficient deoxygenation of sulfoxides to sulfides with Cp 2TiCl2/gallium system
-
The Cp2TiCl2/Ga system was found to be a new reagent for reducing a variety of sulfoxides to the corresponding sulfides in good to excellent yields under mild conditions. Copyright
- Yoo, Byung Woo,Min, Sang Ki
-
body text
p. 2993 - 2996
(2011/09/14)
-
- Polystyrene and silica gel-supported, AlCl3-catalyzed preparation of diaryl sulfoxides from arenes and thionyl chloride
-
A simple, chemoselective, and efficient method has been developed for direct conversion of arenes to symmetrical diaryl sulfoxides using thionyl chloride in the presence of a catalytic amount of cross-linked polystyrene-supported aluminium chloride (Ps-AlCl3) and silica gel-supported aluminium chloride (SiO2-AlCl3). These solid acid catalysts are stable and can be easily recovered and reused without appreciable change in their efficiency. Copyright Taylor & Francis Group, LLC.
- Boroujeni, Kaveh Parvanak
-
scheme or table
p. 2085 - 2091
(2010/12/19)
-
- Aryl sulfoxides from aliyi sulfoxides via [2,3]-sigmatropic rearrangement and domino Pd-catalyzed generation/ arylation of sulfenate anions
-
(Figure presented) Allylic sulfoxides, via [2,3]-sigmatropic rearrangement and oxidative addition of the resulting allylic sulfonate esters to Pd(0), are found to be excellent precursors of sulfenate anions. This hitherto unknown reactivity is applied in a new Pd(0)-catalyzed domino sequence involving sulfonate anion generation followed by arylation to afford aryl sulfoxides.
- Bernoud, Ellse,Le Duc, Gaetan,Bantrell, Xavier,Prestat, Guillaume,Madec, David,Poll, Giovanni
-
supporting information; experimental part
p. 320 - 323
(2010/03/24)
-
- Kinetics and mechanism of (saJen)Mnlll-catalysed hydrogen peroxide oxidation of diphenyl sulphides
-
The kinetics of (salen)MIII complexes-catalysed oxidation of a few diphenyl sulphides by hydrogen peroxide have been investigated at 25°C in acetonitrile (80%) - water (20%) spectrophotometrically. The reaction follows first-order kinetics in (salen)Mn111 complex and zero-order kinetics in hydrogen peroxide. The order of the reaction with respect to .sulphide is fractional. The effects of nitrogenous bases, free radical inhibitor and changes in solvent composition have also been studied. A suitable mechanism involving a manganese(III)-hydroperoxide complex as reactive species has been proposed.
- Chellamani,Alhaji
-
experimental part
p. 346 - 351
(2010/01/16)
-
- Mild and efficient deoxygenation of sulfoxides with MoCl5/indium system
-
It has been demonstrated that dialkyl, diaryl, and aryl alkyl sulfoxides can be efficiently converted into the corresponding sulfides by the reaction with a MoCl5/In system in good to excellent yields under mild conditions. Copyright Taylor & Francis Group, LLC.
- Yoo, Byung Woo,Song, Min Suk,Park, Min Chol
-
p. 3089 - 3093
(2008/02/12)
-
- Oxidation kinetics of some sulfoxides with N,N-dibromobenzene sulfonamide
-
The kinetics of oxidation of some sulfoxides with dibromamine-B yielding sulfones was investigated in presence of HgII, and the rate equation, kobs = k3K2K′h[S]/[RNH 2] + K′h was found to be valid. The reaction involves two distinct pathways namely initial fast step and a subsequent slow step. The chloride ions have no effect on the reactivity of sulfoxides. Sulfoxides containing electron-attracting substituents retard the reactivity while those containing electron-releasing constituents accelerate the rate of oxidation. Exner plot confirms the operation of same mechanism in all the sulfoxides studied. Electrophilic addition of Br+ to sulfur atom results in an electron-deficient sulfonium centre which decomposes in a slow rate-limiting step. The rate coefficients are treated in terms of multiparametric extensions of the Hammett equation to have more insight into the mechanistic aspects.
- Meenakshisundaram, Subbiah,Amutha
-
p. 679 - 682
(2008/09/18)
-
- Aryl sulfoxides via palladium-catalyzed arylation of sulfenate anions
-
(Chemical Equation Presented) Palladium-catalyzed arylation of sulfenate anions generated from β-sulfinyl esters can take place under biphasic conditions. This hitherto unknown reaction provides a simple, mild, and efficient route to aryl sulfoxides in good yields. The development of a new pseudo-domino type I procedure involving a sulfinylation followed by a Mirozoki-Heck coupling is also described.
- Maitro, Guillaume,Vogel, Sophie,Prestat, Guillaume,Madec, David,Poli, Giovanni
-
p. 5951 - 5954
(2007/10/03)
-
- Tetracyanoethylene oxide not only oxidizes sulfides to sulfoxides but also reduces sulfoxides to sulfides
-
It was found that tetracyanoethylene oxide not only oxidizes sulfides to sulfoxides but also reduces sulfoxides to sulfides with generation of two molecules of carbonyl cyanide. The reaction thus also functions as a new method for generation of carbonyl cyanide.
- Nakayama, Juzo,Tai, Ayako,Iwasa, Sachiko,Furuya, Tomohiro,Sugihara, Yoshiaki
-
p. 1395 - 1397
(2007/10/03)
-
- Selective oxidation of sulfides to sulfoxides using 30% hydrogen peroxide catalyzed with a recoverable silica-based tungstate interphase catalyst
-
(Chemical Equation Presented) Various types of aromatic and aliphatic sulfides are selectively oxidized to sulfoxides and sulfones in good to excellent yields using 30% H2O2 in the presence of catalytic amounts of a novel recoverable silica-based tungstate interphase catalyst at room temperature. The catalyst can be recovered and reused for at least eight reaction cycles under the described reaction conditions without considerable loss of reactivity.
- Karimi, Babak,Ghoreishi-Nezhad, Maryam,Clark, James H.
-
p. 625 - 628
(2007/10/03)
-
- An ionic liquid-mediated expeditious route to the syntheses of diaryl sulfoxides
-
A fast and efficient protocol is proposed for the synthesis of diaryl sulfoxides in the ionic liquid 1-butyl-3-methylimidazolium chloroaluminate, [bmim]Cl·AlCl3, N=0.67, by employing arenes and thionyl chloride. The ionic liquid plays a dual role of Lewis acid catalyst and solvent, under ambient conditions, offering good yields of the product. The influence of the Lewis acidity of the ionic liquid on the extent of conversion is studied.
- Mohile, Swapnil S.,Potdar, Mahesh K.,Salunkhe, Manikrao M.
-
p. 1255 - 1258
(2007/10/03)
-
- Highly Rapid and Direct Synthesis of Diaryl Sulfoxides
-
Aromatic compounds react smoothly with thionyl chloride in the presence of 10 mol% of water at ambient temperature to afford the corresponding symmetrical diaryl sulfoxides in good to excellent yields with high regioselectivity.
- Bandgar,Kinkar,Kamble,Bettigeri
-
p. 2029 - 2032
(2007/10/03)
-
- Electrophilic oxidant produced in the photodeoxygenation of 1,2-benzodiphenylene sulfoxide
-
We report that the photodeoxygenation of 1,2-benzodiphenylene sulfoxide, 1, generates an intermediate capable of oxidizing the solvent benzene to phenol. The reactivity of the intermediate was probed with various substrates (2-methylbutane, chloride ion,
- Lucien,Greer
-
p. 4576 - 4579
(2007/10/03)
-
- A selective and convenient oxidation of sulfides to sulfoxides with trichloroisocyanuric acid
-
Sulfides are readily oxidized to sulfoxides by a solution of pyridine, water, and trichloroisocyanuric acid in acetonitrile and methylene chloride.
- Xiong,Huang,Zhong
-
p. 245 - 248
(2007/10/03)
-
- Hypervalent iodine in synthesis XXVIII: The preparation and utility of polymer-supported phenyliodine(III) diacetate
-
The polymer-supported phenyliodine(III) diacetate has been developed, which has been used effectively to oxidize a variety of organic compounds with good yield.
- Wang, Guo-Ping,Chen, Zhen-Chu
-
p. 2859 - 2866
(2007/10/03)
-
- Synthetic use of poly[4-(diacetoxyiodo)styrene] for organic reactions
-
Poly[4-(diacetoxyiodo)styrene] is sufficiently reactive for the iodination of aromatics, the oxidative 1,2-aryl migration of alkyl aryl ketones, the α-hydroxylation of ketones, and the oxidation of hydroquinones and sulfides similarly to (diacetoxyiodo)benzene. Here, those reactions with poly[4-(diacetoxyiodo)styrene] are very useful because of the simple operation; thus, filtration gives the crude products and recovered poly(4- iodostyrene), and then poly[4-(diacetoxyiodo)-styrene] can be regenerated by oxidation of the recovered poly(4-iodostyrene), which are reused for the same reactions.
- Togo, Hideo,Abe, Seiichiro,Nogami, Genki,Yokohama, Masataka
-
p. 2351 - 2356
(2007/10/03)
-
- Trifluoromethanesulfonic acid catalyzed preparation of symmetrical diaryl sulfoxides from arenes and thionyl chloride
-
The preparation of symmetrical diaryl sulfoxides from thionyl chloride and arenes catalyzed by trifluoromethanesulfonic acid is described. The reaction is characterized by its mildness, high yields, selectivity, and ease of workup.
- Olah, George A.,Marinez, Eric R.,Prakash, G. K. Surya
-
p. 1397 - 1398
(2007/10/03)
-
- Phosphadioxirane Intermediates in the Reaction of Singlet Oxygen with Phosphites and Phosphines
-
Intermediates in the singlet oxygen reaction of phosphites and phosphines have been studied by trapping and tracer experiments.Trapping study with diphenyl sulfoxide revealed that the added substrate and phosphite are competing toward the same intermediate.The relative reactivity of (BuO)3P/Ph2S/Ph2SO = 300:4:1 and the negative ρ-value of -0.63 for diphenyl sulfoxides are not consistent with 1,3-dipolar phosphine peroxides, but suggest electrophilic O-transfers by cyclic phosphadioxiranes.Intermediacy of phosphadioxiranes was supported by an 18O-tracer study on the formation of rearranged diphenylphosphinate from 1O2 and triphenylphosphine.Theoretical calculations also supported the dioxirane intermediate by predicting no existence of 1,3-dipolar peroxide.
- Tsuji, Shoei,Kondo, Masaaki,Ishiguro, Katsuya,Sawaki, Yasuhiko
-
p. 5055 - 5059
(2007/10/02)
-
- Reaction of Simple Arenes with FSO3H*SbF5/SO2: One-Pot Synthesis of Aromatic Sulfoxides. Mechanistic Aspects and Synthetic Utility
-
In a simple one-pot reaction, mono-, di-, tri-, and polyalkylbenzenes, isomeric alkylhalobenzenes, and fluoro-, (trifluoromethyl)-, and 1,3,5-trifluorobenzene were converted to their corresponding diaryl sulfoxides with FSO3H*SbF5 (1:1) (magic acid)/SO2.Dependency of the yields on the acidity (H0) and the arene structure was demonstrated.Reduction of the formed sulfoxide was also observed as a minor pathway to give diaryl sulfide.The reduction is superacid-catalyzed, and protonated sulfoxides are the key intermediates en route to sulfides.Protonation of several functionalized diaryl sulfoxides was also studied in magic acid/SO2 under stable ion conditions.Unlike the parent diphenyl sulfoxide, which is S-protonated, alkyl-, fluoro-, and trifluoromethyl-substituted diaryl sulfoxides O-protonate to give long-lived sulfoxonium ions.The proposed mechanism for the arene/superacid/SO2 system involves sulfination of the arenium ions, O-protonation of the resulting sulfinic acid, dehydration of the oxonium ion "ArSO+" and arylation.In the absence of SO2, the fluorosulfonation, ionization, arylation path becomes dominant.The scope of the reaction is sufficiently broad to be synthetically useful.The methodology is also applicable to unsymmetrical (mixed) diaryl sulfoxides.
- Laali, Kenneth Khosrow,Nagvekar, Devdatt S.
-
p. 1867 - 1874
(2007/10/02)
-
- Extremely Facile Ligand-Exchange and Disproportionation Reactions of Diaryl Sulfoxides, Selenoxides, and Triarylphosphine Oxides with Organolithium and Grignard Reagents
-
Diaryl sulfoxides undergo unusually rapid ligand-exchange reaction upon treatment with organolithium reagents at -95 deg C.Optically pure phenyl p-tolyl sulfoxide (4b) reacted with organolithium reagents at the range from -20 to -95 deg C to give facile ligand-exchange and disproportionation products, i.e., diphenyl sulfoxide (7), recovered 4b, and di-p-tolyl sulfoxide (8) in a statistical ratio of 1:2:1 in quantitative yields, and the recovered 4b was completely racemized.This facile ligand exchange was observed in the similar reactions using only diaryl selenoxides and triarylphosphine oxides.The reactions of 18O-labeled phenyl p-tolyl sulfoxide (4c) with organolithium reagents gave products in a statistical ration without 18O scrambling, indicating that only the C-S bond cleavage took place under low temperature.It is suggested that the ligand exchange reactions occur by the nucleophilic attack by organolithium reagent at the sulfinyl sulfur atom, giving ?-sulfurane as an intermediate that collapses rapidly.These results suggest that the treatment of arylic sulfoxides, selenoxides, and phosphine oxides with strong bases should be effected with caution.
- Furukawa, Naomichi,Ogawa, Satoshi,Matsumura, Kazunori,Fujihara, Hisashi
-
p. 6341 - 6348
(2007/10/02)
-
- Selectivity in the TiO2-mediated photocatalytic oxidation of thioethers
-
The relative rates of photooxygenation of substituted diphenyl sulfides on irradiated TiO2 powders suspended in oxygenated acetonitrile correlate linearly with σ+, as is consistent with formation of a surface bound cation radical in the primary photoprocess. Substituted dibenzyl sulfides, in contrast, suffer C-S cleavage upon photocatalyzed oxidation. Factors disposing these reactions toward preferential sulfoxide formation or bond cleavage are discussed.
- Fox,Abdel-Wahab
-
p. 4533 - 4536
(2007/10/02)
-
- Methylation of aromatics with Me3S+, Me3Se+, and Me3Te+ in superacid media
-
Electrophilic reactivity of Me3S+OTf, Me3Se+OTf, and Me3Te+OTf (OTf = trifluoromethanesulfonate) in superacid solvents towards aromatics has been demonstrated, indicative of protosolvation of the remaining lone pair on the onium ions.When dissolved in superacids, Me3Se+OTf and Me3Te+OTf show measurable changes in their NMR (1H, 13C, 77Se, 125Te) chemical shifts and one bond 77Se-13C, 125Te-13C spin-spin coupling constants.The NMR data are compared with those of related selenonium cations and donor-acceptor complexes.
- Laali, Khosrow,Chen, H. Y.,Gerzina, Robert, J.
-
p. 199 - 204
(2007/10/02)
-
- A NEW SOURCE FOR GENERATION OF BENZYNE AND PYRIDYNE: REACTIONS OF O-HALOPHENYL (OR 3-BROMO-4-PYRIDYL) PHENYL SULFOXIDES WITH GRIGNARD REAGENTS
-
o-Chloro- and o-bromophenyl phenyl sulfoxides and (3-bromo-4-pyridyl) phenyl sulfoxide were treated with Grignard reagents to generate benzyne (or 3,4-pyridyne) in THF.The o-iodophenyl derivative, on the other hand, gave mainly o-(arylsulfinyl)phenyl Grignard reagent.
- Furukawa, Naomichi,Shibutani, Tadao,Fujihara, Hisashi
-
p. 2727 - 2730
(2007/10/02)
-
- TURNING THE REACTIVITY OF CARBONYL OXIDES FROM NUCLEOPHILIC TO ELECTROPHILIC. A NOVEL DEOXYGENATION OF SULFOXIDES BY ELECTROPHILIC α,α,α-TRIFLUOROACETOPHENONE O-OXIDE
-
The well-known nucleophilic reactivity of carbonyl oxides could be turned into electrophilic by a potent electron-attracting group.Thus α,α,α-trifluoroacetophenone O-oxide oxidizes both sulfides and sulfoxides electrophilically, and the most characteristic reaction is the deoxyganation of sulfoxides.
- Ishiguro, Katsuya,Hirano, Yukimichi,Sawaki, Yasuhiko
-
p. 6201 - 6204
(2007/10/02)
-
- PHASE TRANSFER CONTROLLED SELECTIVE OXIDATION OF DIARYLSULFIDES TO DIARYLSULFOXIDES USING POTASSIUM HYDROGEN PERSULFATE
-
The use of biphasic reaction conditions and a phase transfer catalyst controls the oxidation reaction of potassium hydrogen persulfate with diarylsulfides yielding predominantly sulfoxides.This is in contrast to the raction in polar solvents where sulfones are the major products.
- Evans, T. L.,Grade, M. M.
-
p. 1206 - 1216
(2007/10/02)
-
- THERMOLYSES AND REACTIONS WITH NUCLEOPHILES OF N-SULFUR-GROUP-SUBSTITUTED SULFOXIMINES
-
Thermolyses and reactions with nucleophiles of S,S-diphenylsulfoximines (1) bearing the following N-sulfur-substituents, i.e., N-p-tolylthio-(b), N-p-tolylsulfinyl-(c), N-(N'-p-tolylsulfonyl-p-toluenesulfinimidoyl)-(d), N-(S',S'-diphenylsulfonio)-(e), N-p-tolylsulfonyl-(f), and N-(N'-p-tolylsulfonyl-p-toluenesulfonimidoyl)-(g), have been examined.The former three sulfoximines (1b-d) are thermally unstable and readily decompose to form diphenyl sulfoxide and diphenyl sulfide by the initial cleavage of the S-N linkage in the original sulfoximines.The latter three sulfoximines (1e-g) fairly stable thermally. 1b-d were found to react with several nucleophiles to afford the corresponding sulfenylated, sulfinylated or sulfinimidoylated products together with N-unsubstituted sulfoximine(1a). 1e was found to react with potassium hydroxide/methanol or chloramine-T/N,N-dimethylformamide to afford diphenyl sulfoxide or S,S-diphenyl-(N-p-tolylsulphonyl)sulfilimine along with 1a in good yields.The latter two sulfoximines (1f,g) were found to be inert in the treatment with a few nucleophiles.S,S-Diphenyl-(N-p-tolylthio)-(1b), -(N-p-tolylsulfinyl)-(1c), -(N-p-toluenesulfinimidoyl)-(1d), and -N-(diphenylsulfonio)-(1e) sulfoximines are all new to sulfoximine chemistry and their chemical behavior and reactivity have not been explored.As a preliminary step, thermal decompositions and reactions of these sulfoximines with several nucleophiles have been examined.
- Oae, Shigeru,Akutagawa, Kunihiko,Furukawa, Naomichi
-
p. 223 - 234
(2007/10/02)
-