- Ionic liquid-functionalized amphiphilic Janus nanosheets afford highly accessible interface for asymmetric catalysis in water
-
High oil/water interfacial area together with accessible interfaces for regents is the key to achieving efficient asymmetric catalysis in water. Herein, by taking advantage of the excellent interfacial activity of Janus nanosheets (JNS), as well as the unique compatibility of imidazolium ionic liquid (IL), we developed a series of IL-functionalized amphiphilic Janus mesosilica nanosheets which afford highly accessible reaction interfaces for highly enantioselective sulfoxidation in water. The JNS-typed chiral salen TiIV catalysts were prepared by selectively decorating hydrophobic chiral salen TiIV complex on one side of Janus mesosilica nanosheets through the imidazolium-based IL linker. Benefiting from the two-dimensional porous Janus structure, as well as the compatible IL linker, the IL-tagged JNS catalysts afforded high oil/water interfacial areas and highly accessible reaction interface for sulfides and H2O2, significantly accelerating asymmetric sulfoxidation in water using H2O2 as an oxidant. In addition, they can be facilely recovered for stable reuse by simple centrifugation.
- Li, Chaoping,Liu, Su,Pi, Yibing,Feng, Jingwen,Liu, Zewei,Li, Shiye,Tan, Rong
-
-
Read Online
- Asymmetric Synthesis of Phenyl Alkyl Sulphoxides via the Non-destructive Mediation of the Chiral Iron Acyl 5-C5H5)Fe(CO)(PPh3)COCH2Me>
-
The chiral sulphoxide (RSS)-5-C5H5)Fe(CO)(PPh3)COCHMeSOPh> can be efficiently and stereoselectively prepared from (R)-5-C5H5)Fe(CO)(PPh3)COCH2Me> via the asymmetric oxidation of the corresponding sulphide: treatment of (RSS)-(
- Davies, Stephen G.,Gravatt, G. Lance
-
-
Read Online
- The Pummerer-type reaction mediated ring-opening of 2-alkyl substituted 1-[(2-methoxyethoxy)methoxy]-2-(phenylsulfinyl)cyclopropanes
-
α-Lithiated 1-[(2-methoxyethoxy)methoxy]-2-(phenylsylfinyl)cyclopropane reacted smoothly with alkylating agents to afford the corresponding α-alkylated cyclopropylsulfoxides, which underwent the Pummerer-type reaction mediated ring-opening at low temperature (-78°C) by employing TFAA/Pri2NEt/CH2Cl2 to give mixtures of β-(phenylthio)-α,β- and γ,δ-unsaturated aldehydes.
- Pohmakotr, Manat,Moosophon, Panawan,Pisutjaroenpong, Somchai,Tuchinda, Patoomratana,Reutrakul, Vichai
-
-
Read Online
- Novel mesoporous polyoxometalate hybrid catalysts for heterogeneous oxidation of thioethers
-
K6P2W18O62 and K 14[NaP5W30O110] polyoxometalate salts are synthesized and immobilized within MCM-48, SBA-3, SBA-15 and NH 3+ functionalized meso
- Karimi,Mahjoub
-
-
Read Online
- Oxidation of organic sulfides with clay-supported iodosylbenzene as oxygen donor
-
Alkyl, aryl and diaryl sulfides afford excellent yields of sulfoxides with PhIO supported on natural (montmorillonite, KSF and bentonite clay) as well as cation-exchanged clays of K10-montmorillonite in acetonitrile suspension and also in solid state. A l
- Kannan, Pothiraj,Sevvel, Ranganathan,Rajagopal, Seenivasan,Pitchumani, Kasi,Srinivasan, Chockalingam
-
-
Read Online
- Selective Oxidation of Sulfides in Flow Chemistry
-
A packed-bed reactor with oxone has been employed for selective oxidations of sulfur compounds. Various sulfides containing different functional groups are efficiently oxidized to the corresponding sulfoxides without formation of sulfones or other side products.
- Silva, Filipa,Baker, Alastair,Stansall, James,Michalska, Weronika,Yusubov, Mehkman S.,Graz, Michael,Saunders, Robert,Evans, Gareth J. S.,Wirth, Thomas
-
-
Read Online
- Light-controlled cooperative catalysis of asymmetric sulfoxidation based on azobenzene-bridged chiral salen TiIVcatalysts
-
Incorporation of azobenzene into the linker of bimetallic chiral salen TiIVcatalysts allowed the photoswitchable arrangement of the two Ti(salen) units throughcis/transphotoisomerization of azobenzene. The differently arranged Ti(salen) units changed their cooperative function to reflect the positional relationships, as a result, their efficiency as cooperative catalysts in asymmetric sulfoxidation could be readily controlled by light stimuli.
- Fu, Wenqin,Gao, Mengqiao,Li, Chaoping,Pi, Yibing,Tan, Rong,Wang, Weiying,Yin, Donghong
-
-
Read Online
- Aminoxidation of Arenethiols to N-Chloro-N-sulfonyl Sulfinamides
-
A simple and efficient method to synthesize N-chloro-N-sulfonylsulfinamides by the direct aminoxidation of arenethiols under aqueous and mild conditions is disclosed, geminally installing the oxo and amino groups on the sulfur atom of arenethiols. The products have been primarily developed as sulfinylation reagents to convert Grignard reagents into sulfoxides, and as amination reagents to convert secondary amines into hydrazine derivatives.
- Yang, Zhanhui,Xu, Wei,Wu, Qiuyue,Xu, Jiaxi
-
-
Read Online
- Efficient and convenient oxidation of sulfides to sulfoxides with molecular oxygen catalyzed by Mn(OAc)2 in ionic liquid [C12mim][NO3]
-
A simple, efficient, and eco-friendly procedure for aerobic oxidation of sulfides catalyzed by Mn(OAc)2/[C12mim][NO3] has been developed. The reactions afford the target products in good to high yields and no over-oxidatio
- Hu, Yu-Lin,Fang, Dong,Xing, Rong
-
-
Read Online
- Selective oxidation of sulfides to sulfoxides with poly[4-hydroxy(tosyloxy) iodo]styrene
-
Sulfides can be selectively converted to corresponding sulfoxides in excellent yields under mild conditions by linear and 1% cross-linked poly[4-hydroxy(tosyloxy)iodo]styrene (PSHTIB). Copyright Taylor & Francis, Inc.
- Liu, Ping,Liu, Shi-Juan,Zhang, Ji-Zhen,Tian, Guan-Rong
-
-
Read Online
- Biocatalytic Oxidation of Sulfides to Sulfones
-
This paper describes a method for the biocatalytic oxidation of sulfides. During the screening of microorganisms using pure cultures of bacteria and fungi for the oxidation of sulfides, it was observed that a number of strains of microorganisms, were able to oxidize various sulfides (1-4), but the desired sulfoxide was either not obtained or obtained only as a minor product. A close observation of the reaction showed complete oxidation and thus sulfone (5-8) formation had occurred in these cases. Sulfones are used to stabilize intermediates like α-radicals, α-anions etc. and also used as cationic synthons in many known reactions. This prompted us to explore the sulfone synthesis by biocatalytic route. Approximately 20% of the strains tested (400 bacterial and 200 fungal) showed the formation of sulfone with conversion rate varying from 3 to 100% based on TLC analysis. There were two strains of fungi, Aspergillus ochraceus MTCC 5245 and Penicillium Funiculosum MTCC 5246 which showed excellent biocatalytic activity for oxidation sulfides to corresponding sulfones in high yield. In all these strains, the product was different from corresponding standard sulfoxide prepared by oxidation with m-chloroperbenzoic acid but well corresponded with the standard sample of sulfone prepared by oxidation of the corresponding sulfides with oxone. The identity of sulfones in all cases was confirmed by 1H NMR. Published by Oriental Scientific Publishing Company
- Dhiman, Shefali
-
p. 250 - 255
(2021/03/29)
-
- Highly efficient and selective aqueous aerobic oxidation of sulfides to sulfoxides or sulfones catalyzed by tungstate-functionalized nanomaterial
-
A Br?nsted acidic ionic solid comrising tungstate-functionaized polyorganosiloxane framework (PMO-IL-WO42?) efficiently catalysed aerobic oxidation of sulfides in aqueous medium. The catalyst can selectively produce sulfoxides or sulfones by running the reaction at room temperature or 50 °C, respectively. Because of the ionic liquid-based charged surface containing hydrophobic organic functional groups and hydrophilic sulfonic acid group, the synergestic hydrophobic/hydrophilic and redox effect of PMO-IL-WO42- as water-friendly interfacial nanocatalyst simplifies and enhances the activity and selectivity toward the target sulfoxides or sulfones in water. Moreover, the PMO-IL-WO42- nanocatalyst exhibited outstanding stability and activity and can be recycled eight reaction runs without any significant activity and selectivity loss.
- Luque, Rafael,Rajabi, Fatemeh,Vessally, Esmail,Voskressensky, Leonid
-
-
- An ionic liquid-functionalized amphiphilic Janus material as a Pickering interfacial catalyst for asymmetric sulfoxidation in water
-
Ionic liquid-functionalized amphiphilic Janus chiral salen TiIV catalysts were prepared by partial hydrophobic modification of silica with a chiral salen TiIV complex through an imidazolium ionic liquid (IL) linker. By optimizing their hydrophobic/hydrophilic balance, the IL-functionalized JNP materials exhibited excellent interfacial activity, significantly accelerating asymmetric sulfoxidation in water through the formation of stable Pickering emulsions. Moreover, catalyst recovery was readily achieved using centrifugation.
- Zhang, Mingjie,Tang, Zhiyang,Fu, Wenqin,Wang, Weiying,Tan, Rong,Yin, Donghong
-
supporting information
p. 592 - 595
(2019/02/05)
-
- Design, synthesis and antiplasmodial evaluation of sulfoximine-triazole hybrids as potential antimalarial prototypes
-
Background: Malaria, caused by the deadly Plasmodium falciparum strain, claims the lives of millions of people annually. The emergence of drug-resistant strains of P. falciparum to the artemisinin-based combination therapy (ACT), the last line of defense against malaria, is worrisome and urges for the development of new chemo-types with a new mode of action. In the search of new antimalarial agents, hybrids of triazoles and other known antimalarial drugs have been reported to possess better activity than either of the parent compounds administered individually. Despite their better activity, no hybrid antimalarial drugs have been developed so far. Objective: In the hope of developing new antimalarial prototypes, we propose the design, synthesis and antimalarial evaluation of novel sulfoximine-triazole hybrids owing to their interesting biological and physiological properties. Method: The sulfoximine part of the hybrid will be synthesized via imidation of the corresponding sulfoxide. Propargylation of the NH moiety of the sulfoximine followed by copper-catalyzed click chemistry with benzyl azide was envisaged to provide the target sulfoximine-triazole hybrids. Results: Five novel sulfoximine-triazole hybrids possessing various substituents on the sulfoximine moiety have been successfully synthesized and evaluated for their antiplasmodial and cytotoxicity activities. The results revealed that the co-presence of the sulfoximine and triazole moieties along with a lipophilic alkyl substituent on the sulfur atom impart significant activity. Conclusion: Sulfoximine-triazole hybrids could be used as a prototype for the synthesis of new derivatives with better antiplasmodial activities.
- Mabasa, Tommy Fredrick,Awe, Babatunde,Laming, Dustin,Kinfe, Henok Hadgu
-
p. 683 - 690
(2019/08/30)
-
- Ullmann-type: N-arylation of anilines with alkyl(aryl)sulfonium salts
-
A palladium/copper-cocatalyzed Ullmann-type N-arylation of anilines using alkyl(aryl)sulfonium triflates as arylation reagents has been accomplished. The reaction enabled Caryl-S bond cleavage over Calkyl-S bond breakage of alkyl(aryl)sulfoniums by Pd(P(tBu)3)2/CuI and gave the corresponding N-arylated products in good to high yields. It was also significant that the reactions of aniline with asymmetric butyl(mesityl)(aryl)sulfonium triflates showed excellent selectivity, in which the aryl groups other than the bulky and electron-rich mesityl moieties were transformed.
- Tian, Ze-Yu,Zhang, Cheng-Pan
-
p. 11936 - 11939
(2019/10/11)
-
- Magnetic core-shell nanoparticle-supported Sc (III): A novel and robust Lewis acid nanocatalyst for the selective oxidation of sulfides to sulfoxides by H2O2 under solvent-free conditions
-
For the first time scandium triflate was supported on modified Fe3O4 magnetic nanoparticles [MNPs-PhSO3-Sc(OTf)2] and characterized using scanning electron microscopy (SEM), inductively coupled plasma analysis (
- Khaledian, Donya,Rostami, Amin,Rouhani, Shamileh
-
-
- Titanium(iv)-folded single-chain polymeric nanoparticles as artificial metalloenzyme for asymmetric sulfoxidation in water
-
Intrachain TiIV-oxazoline complexation together with hydrophobic interaction triggered the self-folding of an oxazoline-containing single polymeric chain in water. The formed TiIV-folded single-chain polymeric nanoparticles (SCPNs) acted as metalloenzyme-mimetic catalysts in asymmetric sulfoxidation in water owing to their organized, compartmentalized structure, effective site isolation, and also secondary coordination sphere provided by a copolymer backbone. In addition, they also could be facilely recovered for reuse by simple thermo-controlled separation.
- Zhang, Yaoyao,Wang, Weiying,Fu, Wenqin,Zhang, Mingjie,Tang, Zhiyang,Tan, Rong,Yin, Donghong
-
supporting information
p. 9430 - 9433
(2018/08/28)
-
- Green route for selective gram-scale oxidation of sulfides using tungstate/triazine-based ionic liquid immobilized on magnetic nanoparticles as a phase-transfer heterogeneous catalyst
-
Tungstate ions were successfully loaded onto triazine-based ionic liquid-functionalized magnetic nanoparticles through an anion exchange process. The use of triazine core for creating ionic liquid led to the immobilization of high amounts of WO4/sub
- Hosseini, Seyed Hassan,Tavakolizadeh, Maryam,Zohreh, Nasrin,Soleyman, Rouhollah
-
-
- Simple low cost porphyrinic photosensitizers for large scale chemoselective oxidation of sulfides to sulfoxides under green conditions: Targeted protonation of porphyrins
-
Aerobic photooxidation of sulfides with the diacids of meso-tetra(phenyl)porphyrin, H2TPP (acid = CF3COOH, Cl2CHCOOH, HClO4 and H2SO4) under sunlight in acetonitrile gave the corresponding sulfoxides as nearly the exclusive product. The photocatalytic activity of the dications decreased as H4TPP(ClO4)2 ? H4TPP(Cl2CHCOO)2 ? H4TPP(CF3COO)2 > H4TPP(HSO4)2. Also, H4TPP(ClO4)2 and H4TPP(Cl2CHCOO)2 showed a remarkably increased oxidative stability in comparison with the free base porphyrin. The singlet oxygen quantum yield (φΔ) of the porphyrin diacids was found to be dependent on the acid used for the protonation of H2TPP. The solvent effect on the efficiency of the oxidation reaction was investigated using acetonitrile, 1,2-dichloroethane (DCE) and toluene. The higher conversions achieved in acetonitrile and DCE are in accord with the higher singlet oxygen lifetime in these solvents. Also, the lower fluorescence quantum yield of porphyrin dications in acetonitrile relative to that in DCE was used to explain the higher efficiency of the former. The porphyrin diacids can also accelerate the oxidation reaction through an acid catalysis mechanism. Also, cooxidation of methyl phenyl sulfide and diphenyl sulfide was conducted to provide insights into the nature of the active intermediates involved in the oxidation of sulfides to sulfoxides and partial overoxidation of the sulfoxides to sulfones. The results showed much higher reactivity of the persulfoxide intermediate compared to that of singlet oxygen. The catalytic system was successfully employed to the large scale preparation of sulfoxides from the corresponding sulfides under mild conditions.
- Mojarrad, Aida G.,Zakavi, Saeed
-
p. 768 - 781
(2018/02/14)
-
- Oxygenation of sulfides catalysed by SBA-15-immobilized molybdenum(VI) complex of a bis(phenol) diamine ligand using aqueous hydrogen peroxide as a green oxidant
-
A highly efficient and reusable molybdenum-based catalyst has been synthesized by covalent grafting of a bis(phenol) diamine ligand, namely 2-(((2-bromoethyl)(2-((3,5-di-tert-butyl-2-hydroxybenzyl)amino)ethyl)amino)methyl)-4,6-di-tert-butylphenol, onto functionalized ordered mesoporous silica (SBA-15) followed by complexation with MoO2(acac)2. The resulting organic–inorganic hybrid material was found to be a highly effective catalyst for oxygenation of various sulfides to their corresponding sulfoxides or sulfones. The catalyst was characterized using transmission and scanning electron microscopies, X-ray photoelectron, Fourier transform infrared and atomic absorption spectroscopies, Brunauer–Emmett–Teller surface area analysis and thermogravimetric analysis. Mild reaction conditions, high selectivity and easy recovery and reusability of the catalyst render the presented protocol very useful for addressing industrial needs and environmental concerns.
- Saberikia, Iraj,Safaei, Elham,Karimi, Babak,Lee, Yong-Iii
-
-
- Enantioseparation of Sulfoxides and Nitriles by Inclusion Crystallization with Chiral Organic Salts Based on l-Phenylalanine
-
Enantioselective inclusion of aromatic sulfoxides and nitriles was achieved in a host framework created by organic salts comprising achiral benzoic acids and a chiral primary amine (1a) derived from l-phenylalanine. Tuning of the combined achiral acid component successfully changed the chiral recognition ability of the organic salts. The guest molecules were hydrogen-bonded to form three-component inclusion crystals, and the enantiomers of nitriles and sulfoxides were separated with high selectivity up to 92 and 98 % ee. As far as we know, this is the first example of the enantioseparation of non-functionalized aromatic nitriles.
- Kodama, Koichi,Kanai, Hayato,Shimomura, Yuki,Hirose, Takuji
-
supporting information
p. 1726 - 1729
(2018/04/24)
-
- Iron(III) Amine Bis(phenolate) Complex Immobilized on Silica-Coated Magnetic Nanoparticles: A Highly Efficient Catalyst for the Oxidation of Alcohols and Sulfides
-
We aimed to immobilize a complex of iron(III) amine bis(phenolate) on silica-coated magnetic nanoparticles as a new magnetically recoverable catalyst (Fe3O4@SiO2-APTES-FeLGDC). Both the chemical nature and the structure of catalyst were confirmed by using field-emission transmission electron microscopy, field-emission scanning electron microscopy, FTIR spectroscopy, thermogravimetric analysis, vibrating sample magnetometry, X-ray photoelectron spectroscopy, XRD, atomic absorption spectroscopy, and elemental analysis. This sustainable catalyst leads to the efficient oxidation of a wide range of alcohols and sulfides with excellent conversion and selectivity under a mild conditions to their corresponding oxidized products, acids (or ketones) and sulfoxides, respectively. Furthermore, the stability of the structure and morphology of our efficient recyclable system was investigated, and all of the data proved that the complex was anchored firmly to the magnetite nanoparticles.
- Karimpour, Touraj,Safaei, Elham,Karimi, Babak,Lee, Yong-Ill
-
p. 1889 - 1899
(2018/01/04)
-
- Asymmetric Sulfinylations of N-Methylephedrine-Modified Tri- or Tetraalkyl Zincates by Symmetric Diaryl Sulfoxides
-
Diethylzinc was treated with 1 or 2 equiv. of AlkMgCl or PhMgBr (preferably) or with 1 equiv. of nBuLi (less efficiently) for forming species – plausibly zincates – which were sulfinylated by diaryl sulfoxides to give racemic alkyl aryl sulfoxides in yields reaching 100 %. Dialkylzinc reagents were also activated by treatments with 1 or 2 equiv. of an enantiomerically pure alkylmagnesium β-aminoalkoxide. This worked best when the alkoxide stemmed from a dialkylmagnesium reagent and an equimolar amount of N-methyl-(–)-ephedrine. This second activation mode allowed sulfinylations of what was originally the dialkylzinc reagent with diaryl sulfoxides. This generated alkyl aryl sulfoxides with enantiomeric ratios up to 93:7 in up to 100 % yield.
- Ruppenthal, Simon,Brückner, Reinhard
-
p. 2518 - 2530
(2018/06/11)
-
- One-pot synthesis of α-phenylsulfinyl ketones by reaction of phenyl benzenethiosulfinate with enolate anions, and synthesis of sulfoxides and sulfides by its reaction with Grignard reagents
-
Phenyl benzenethiosulfinate reacts with enolate anions derived from ketones to give α-phenylsulfinyl ketones directly, together with minor amounts of α-phenylsulfanyl ketones. These are easily separated by forming the water-soluble sodium salts of the sulfinyl compounds. Grignard reagents also react with phenyl benzenethiosulfinate, to give mixtures of sulfoxides and sulfides.
- Fakhry, Jerome,Grayson, David H.
-
p. 556 - 563
(2017/12/28)
-
- Schiff base complex of Mo supported on iron oxide magnetic nanoparticles (Fe3O4) as recoverable nanocatalyst for the selective oxidation of sulfides
-
In this work, a new tridentate Schiff base dioxo-molybdenum(VI) complex immobilized on silica-coated magnetic nanoparticles (MoO25CML–Fe3O4@SiO2) has been synthesized and characterized using different techniques such as FTIR, TGA, AAS, ICP–AES, XRD, VSM, EDX and SEM analyses. The catalytic activity of synthesized complex was examined in the oxidation of various sulfides in the presence of H2O2 as cheap, green and eco-friendly oxidant. This catalytic system provides high conversion and selectivity toward either sulfoxides or sulfones under different conditions. Also, the nanocatalyst could be easily separated and regenerated from reaction media by external magnet and could be reused for ten times without significant loss of the activity and selectivity.
- Aghajani, Milad,Monadi, Niaz
-
p. 963 - 975
(2017/03/11)
-
- ION PAIR CATALYSIS OF TUNGSTATE AND MOLYBDATE
-
D The present invention relates to ion pair catalysts (I) comprising the cationic bisguanidinium ligand (A) and diperoxomolybdate anion (B). The present invention also relates to ion pair catalysts (III) comprising the cationic bisguanidinium ligand (C) and peroxotungstate anion (D). It further relates to the use of the said catalysts in the manufacture of enantiomerically enriched sulfoxides.
- -
-
Page/Page column 41-42; 57
(2017/10/30)
-
- Bio-inspired single-chain polymeric nanoparticles containing a chiral salen TiIV complex for highly enantioselective sulfoxidation in water
-
A series of bio-inspired single-chain polymeric nanoparticles (SCPNs) containing a chiral salen TiIV complex in their hydrophobic cavity were constructed from the synthesized amphiphilic copolymers of poly(NIPAAm-co-IL/Ti(salen)) (NIPAAm, N-isopropylacrylamide; IL/Ti(salen), vinylimidazolium ionic liquid-modified chiral salen TiIV complex). These SCPNs behaved as enzyme-mimetic catalysts due to compartmentalization and site isolation, mediating enantioselective oxidation of various sulfides in water with excellent yields (90-99%) and enantioselectivities (ee, 88-99%). In particular, the ee values observed for electron-rich substrates (>95% ee) represented the best results so far in titanium-salen systems. Moreover, the catalysts could be easily recovered for steady reuse by thermo-controlled separation due to thermo-responsive properties. This work first constructed titanium-containing biomimetic SCNPs for biocatalysis of enantioselective sulfoxidation in water.
- Zhang, Yaoyao,Tan, Rong,Gao, Mengqiao,Hao, Pengbo,Yin, Donghong
-
p. 1182 - 1193
(2017/08/14)
-
- 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.
-
p. 2086 - 2089
(2016/06/01)
-
- Magnetically separable chicken feathers: A biopolymer based heterogeneous catalyst for the oxidation of organic substrates
-
Magnetically separable poultry chicken feathers were found to be an efficient, green and heterogeneous catalyst for the oxidation of alcohols and sulfides to the corresponding carbonyl compounds and sulfoxides, respectively using t-butyl hydroperoxide (TBHP) as oxidant with complete selectivity and high conversions. The developed catalyst exhibited higher stability, activity and better recycling ability than the bare magnetic nanoparticles. The designed catalyst could readily be recovered using an external magnet without showing any significant leaching during the reaction.
- Patnam, Padma L.,Bhatt, Mukesh,Singh, Raghuvir,Saran, Sandeep,Jain, Suman L.
-
p. 60888 - 60895
(2016/07/11)
-
- Metal-Free, Phosphonium Salt-Mediated Sulfoximination of Azine N-Oxides: Approach for the Synthesis of N-Azine Sulfoximines
-
Herein, we report a simple and metal-free method for the synthesis of N-azine sulfoximines by the nucleophilic substitution of azine N-oxides with NH-sulfoximines. The present method works at room temperature with wide functional group compatibility and gives several unprecedented N-azine sulfoximines. The reaction conditions were also found suitable with enantiopure substrates and furnished products without any racemization. It also finds an application in the sulfoximination of azine-based functional molecules such as 2,2′-bipyridine, 1,10-phenanthroline, and quinine.
- Aithagani, Sravan Kumar,Kumar, Mukesh,Yadav, Mahipal,Vishwakarma, Ram A.,Singh, Parvinder Pal
-
p. 5886 - 5894
(2016/07/23)
-
- Formation of Ternary Inclusion Crystal and Enantioseparation of Alkyl Aryl Sulfoxides by the Salt of Urea-Modified l -Phenylalanine and an Achiral Amine
-
Chiral supramolecular hosts comprising urea-modified l-phenylalanines and achiral primary amines were developed, which facilitated enantioselective inclusion of alkyl aryl sulfoxides (3) up to 89% ee owing to the formation of ternary inclusion crystals. F
- Kodama, Koichi,Morita, Rina,Hirose, Takuji
-
p. 5206 - 5213
(2016/11/05)
-
- Enantioselective Sulfoxidation Catalyzed by a Bisguanidinium Diphosphatobisperoxotungstate Ion Pair
-
The first enantioselective tungstate-catalyzed oxidation reaction is presented. High enantioselectivities were achieved for a variety of drug-like phenyl and heterocyclic sulfides under mild conditions with H2O2, a cheap and environmentally friendly oxidant. Synthetic utility was demonstrated through the preparation of (S)-Lansoprazole, a commercial proton-pump inhibitor. The active ion-pair catalyst was identified to be bisguanidinium diphosphatobisperoxotungstate using Raman spectroscopy and computational studies.
- Ye, Xinyi,Moeljadi, Adhitya Mangala Putra,Chin, Kek Foo,Hirao, Hajime,Zong, Lili,Tan, Choon-Hong
-
supporting information
p. 7101 - 7105
(2016/07/06)
-
- Application of 1,4-bis(3-methylimidazolium-1-yl)butane ditribromide [bMImB]·(Br3)2 ionic liquid reagent for selective oxidation of sulfides to sulfoxides
-
1,4-Bis(3-methylimidazolium-1-yl)butane ditribromide [bMImB]·(Br3)2 as an efficient reagent is used for the selective oxidation of dialkyl and alkyl aryl sulfides to the corresponding sulfoxides in high yields under mild conditions. The products can easily be isolated by just washing the highly water soluble 1,4-bis(3-methylimidazolium-1-yl)butane ditribromide [bMImB]·(Br3)2. The spent reagent can be recovered several times and reused without any significant loss.
- Manesh, Abbas Amini,Eshbala, Fereshteh Hosseini,Hemmati, Saba,Veisi, Hojat
-
p. 70265 - 70270
(2015/09/07)
-
- Polymeric ionic liquid nanogel-anchored tungstate anions: A robust catalytic system for oxidation of sulfides to sulfoxides
-
A new heterogeneous catalytic system was prepared by immobilization of tungstate ions on a cross-linked poly(ionic liquid) nanogel. The solid nanogel was easily synthesized by a surfactant-less method. The resulting catalyst was highly active in selective
- Pourjavadi, Ali,Nazari-Chamazkoti, Mojtaba,Hosseini, Seyed Hassan
-
p. 1348 - 1354
(2015/02/19)
-
- Tungstate supported on periodic mesoporous organosilica with imidazolium framework as an efficient and recyclable catalyst for the selective oxidation of sulfides
-
Abstract A catalyst based on immobilization of tungstate ions (WO42-) inside the mesochannels of periodic mesoporous organosilica comprising bridged ionic liquid (1,3-bis(3-trimethoxysilylpropyl)imidazolium chloride) has been synthesized and characterized. This catalyst was then employed for the selective oxidation of organic sulfides to the corresponding sulfoxides or sulfones. The final synthesized catalyst was characterized by various techniques such as nitrogen sorption analysis, transmission electron microscopy, and thermogravimetric analysis. The catalyst was also applied to the selective oxidation of sulfides containing readily oxidizable functional groups such as hydroxyl, allylic, and even challenging aliphatic sulfides. Interestingly, it was found that on changing the reaction medium from aqueous methanol to aqueous acetonitrile, the product selectivity was changed successfully from sulfoxide to sulfone with good to excellent yields. Moreover, the catalyst can also be recovered and reused efficiently in nine subsequent reaction cycles without any remarkable decrease in the catalyst activity and selectivity.
- Karimi, Babak,Khorasani, Mojtaba,Bakhshandeh Rostami, Fatemeh,Elhamifar, Dawood,Vali, Hojatollah
-
p. 990 - 999
(2015/06/08)
-
- Metal-Free Approach for the Synthesis of N-Aryl Sulfoximines via Aryne Intermediate
-
A metal-free and operationally simple N-arylation of NH-sulfoximines with aryne precursors is reported. Transition metal-free reaction conditions and shorter reaction times are the highlights of the present method. The mild optimized condition was also found to be suitable with enantiopure substrates.
- Aithagani, Sravan Kumar,Dara, Saidulu,Munagala, Gurunadham,Aruri, Hariprasad,Yadav, Mahipal,Sharma, Shweta,Vishwakarma, Ram A.,Singh, Parvinder Pal
-
supporting information
p. 5547 - 5549
(2015/12/01)
-
- pH-dependence of the aqueous phase room temperature Br?nsted acid-catalyzed chemoselective oxidation of sulfides with H2O2
-
A pH-dependence of the Br?nsted acid-catalyzed oxidation of sulfides to the corresponding sulfoxides with H2O2 is reported for the first time based on our systematic investigation of the catalytic performance of a series of Br?nsted acids. For all of the Br?nsted acids investigated, the catalytic performances do not depend on the catalyst loading (mol ratio of Br?nsted acid to substrate), but rather depend on the pH value of the aqueous reaction solution. All of them can give more than 98% conversion and selectivity in their aqueous solution at pH 1.30, no matter how much the catalyst loading is and what the Br?nsted acid is. This pH-dependence principle is a very novel perspective to understand the Br?nsted-acid catalysis system compared with our common understanding of the subject.
- Shen, Hai-Min,Zhou, Wen-Jie,Ma, Xin,Wu, Hong-Ke,Yu, Wu-Bin,Ai, Ning,Ji, Hong-Bing,Shi, Hong-Xin,She, Yuan-Bin
-
p. 16709 - 16722
(2015/12/01)
-
- Symmetric diarylsulfoxides as asymmetric sulfinylating reagents for dialkylmagnesium compounds
-
At -78 °C, primary dialkylmagnesium compounds reacted with diarylsulfoxides when 1.5 equiv of the dilithium salt of (S)-BINOL was added as a promotor. Alkyl aryl sulfoxides resulted in up to quantitative yield and with up to 97% ee. This demonstrates the feasibility of asymmetric sulfinylations by achiral sulfinylating agents (from the perspective of Alkyl2Mg) as well as the feasibility of asymmetric sulfoxide-magnesium exchanges (from the perspective of Ar2SO).
- Ruppenthal, Simon,Brückner, Reinhard
-
supporting information
p. 897 - 910
(2015/01/30)
-
- On the nature of the chain-extending species in organolithium initiated stereospecific reagent-controlled homologation reactions using α-chloroalkyl aryl sulfoxides
-
The reaction of an organolithium with an α-chloroalkyl aryl sulfoxide ostensibly generates an α-chloroalkyllithium by sulfoxide-lithium exchange, but the actual identity of the chain-extending species in chlorosulfoxide-based StReCH reactions is not certain. To explore this issue, racemic 2-cyclohexyl (4R?,5R?)-4,5-diphenyl-1,3,2-dioxaborolane was homologated by treatment with scalemic (S)-chloromethyl phenyl sulfoxide and n-BuLi (THF, -78 °C). The reaction proceeded without a detectable level of kinetic resolution, a finding consistent with chloromethyllithium being the active chain-extending species rather than a chiral sulfurane intermediate.
- Hoyt, Amanda L.,Blakemore, Paul R.
-
p. 2980 - 2982
(2015/06/02)
-
- Ammonium salt catalyzed oxidation of organosulfides to organosulfoxydes
-
The selective oxidation of aromatic and aliphatic organosulfides with H2O2/H2O catalyzed by metal free ammonium salts has been explored. Reactions were performed using 2.5-5 mol % of catalyst loadings, isolating the corres
- Secci, Francesco,Frongia, Angelo,Piras, Pier Paolo
-
p. 603 - 605
(2014/01/23)
-
- Iron-catalyzed imidative kinetic resolution of racemic sulfoxides
-
Kinetic resolution of racemic sulfoxides requires either custom substrates or shows moderate enantioselectivity, leading to achiral coproducts (such as sulfones) as an intrinsic part of the process. A new strategy is demonstrated that allows the resolution of racemic sulfoxides through catalytic asymmetric nitrene-transfer reactions. This approach gives rise to both optically active sulfoxides and highly enantioenriched sulfoximines. By using a chiral iron catalyst and a readily available iodinane reagent, high selectivity factors have been achieved under very practical reaction conditions. With respect to the substrate scope, it is noteworthy that this unprecedented imidative kinetic resolution of racemic sulfoxides provides access to both aryl-alkyl and dialkyl sulfoximines in highly enantioenriched forms. Copyright
- Wang, Jun,Frings, Marcus,Bolm, Carsten
-
supporting information
p. 966 - 969
(2014/02/14)
-
- Sulfinylnitriles: Sulfinyl-metal exchange-alkylation strategies
-
Adding organolithiums, Grignard reagents, or zincates to sulfinylnitriles triggers a facile sulfinyl-metal exchange to afford N- or C-metalated nitriles. Sulfinyl-magnesium exchange-alkylations efficiently install quaternary and tertiary centers, even in
- Nath, Dinesh,Fleming, Fraser F.
-
p. 2023 - 2029
(2013/03/14)
-
- Selectivity adjustment of SBA-15 based tungstate catalyst in oxidation of sulfides by incorporating a hydrophobic organic group inside the mesochannels
-
A novel heterogeneous catalyst system comprising tungstate ions embedded into the hydrophobic mesochannels of SBA-15 was found to exhibit significant selectivity enhancement in oxidation of sulfides in water or water/CH 3CN using 30% H2O2. Our studies demonstrated that the presence of an n-octyl group in the interior of nanospaces of our catalyst system provides a hydrophobic/hydrophilic region in the mesochannels of the catalyst where the active tungstate species are located and in turn results in at least three distinct important features. First of all, the catalyst comprising the n-octyl group shows much better water tolerance than the catalysts not having hydrophobic organic moieties. Moreover, the nonproductive decomposition of H2O2 was significantly inhibited in the present catalyst system. The present catalyst system also offers an unprecedented selectivity changeover depending on the hydrophobic nature of the initial sulfides and/or the utilized solvent mixture. While high yields and excellent selectivities toward the corresponding sulfoxide were obtained in the oxidation of less hydrophobic sulfides in H2O as a reaction solvent, the selectivity pattern was shifted toward sulfones in the case of using more hydrophobic sulfides as substrates. On the other hand, in CH3CN/ H2O (1:1) as the reaction solvent, almost all of the studied sulfides were selectively oxidized to the corresponding sulfoxide in high yields. On the basis of several compelling observations, we have proposed a synergistic model to explain the origin of the observed selectivities. The catalyst was respectively recovered and reused in five and seven successive reaction runs in water and water/CH3CN, respectively, with only a slight decrease of reactivity.
- Karimi, Babak,Khorasani, Mojtaba
-
p. 1657 - 1664
(2013/07/26)
-
- Application of a novel 1,3-diol with a benzyl backbone as chiral ligand for asymmetric oxidation of sulfides to sulfoxides
-
A chiral 1,3-diol with a benzyl backbone has been used for the asymmetric oxidation of sulfides to sulfoxides. Moderate to good yields and enantioselectivity (upto 87% ee) have been observed.
- Gogoi, Paramartha,Kotipalli, Trimurthulu,Indukuri, Kiran,Bondalapati, Somasekhar,Saha, Pipas,Saikia, Anil K.
-
supporting information; experimental part
p. 2726 - 2729
(2012/07/17)
-
- Asymmetric counteranion-directed iron catalysis: A highly enantioselective sulfoxidation
-
A highly active and enantioselective ion-pair sulfoxidation catalyst, consisting of an achiral iron(III)-salen cation and a chiral phosphate counteranion, mediates the oxidization of various sulfides with high yields and enantioselectivities. The enantioselectivities observed, especially for electron-poor substrates, represent the best results so far in manganese and iron-salen systems. This work represents the first application of our concept of asymmetric counteranion-directed catalysis (ACDC) to iron catalysis. Copyright
- Liao, Saihu,List, Benjamin
-
supporting information
p. 2363 - 2367
(2012/10/30)
-
- Sulfonated condensed polynuclear aromatic (S-COPNA)) resin catalyzed selective oxidation of sulfides to sulfoxides or sulfones using hydrogen peroxide
-
Sulfonated condensed polynuclear aromatic (S-COPNA) resin was found to be a highly efficient, environmentally friendly, recyclable heterogeneous catalyst for the oxidation of alkyl and aryl sulfides to the corresponding sulfoxides or sulfones, in good yields under mild reaction conditions using 30% hydrogen peroxide as an oxidant. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: Synthesis of the S-COPNA resin catalyst. Spectroscopic data for compounds.
- Shokrolahi, Arash,Zali, Abbas
-
experimental part
p. 454 - 460
(2012/04/17)
-
- Metalloporphyrin-catalyzed chemoselective oxidation of sulfides with polyvinylpyrrolidone-supported hydrogen peroxide: A simple catalytic system for selective oxidation of sulfides to sulfoxides
-
Room temperature oxidation of organic sulfides with polyvinylpyrrolidone- supported hydrogen peroxide (PVP-H2O2) in the presence of Mn(III) complexes of meso-tetraphenylporphyrin, Mn(TPP)X (X = OCN, SCN, OAc, Cl) and imidazole (ImH)
- Zakavi, Saeed,Abasi, Azam,Pourali, Ali Reza,Talebzadeh, Sadegh
-
experimental part
p. 35 - 38
(2012/03/10)
-
- Synthesis, characterization and application of nano-sized Co 2CrO4 spinel catalyst for selective oxidation of sulfides to sulfoxides
-
The nano-sized Co2CrO4 spinel was produced for the first time by thermal decomposition of Cr-Co gel prepared by sol-gel method. It was shown that well-crystallized spinel structure is formed after calcination at 450 °C. The usual cha
- Yazdanbakhsh, Mohammad,Khosravi, Iman,Mashhoori, Mahboobeh-Sadat,Rahimizadeh, Mohammad,Shiri, Ali,Bakavoli, Mehdi
-
experimental part
p. 413 - 418
(2012/03/12)
-
- Efficient and highly selective aqueous oxidation of sulfides to sulfoxides at room temperature catalysed by supported iron oxide nanoparticles on SBA-15
-
The present manuscript describes a simple, efficient and environmentally friendly room temperature aqueous catalytic approach to the selective preparation of sulfoxides from sulfides utilising low-loaded supported iron oxide nanoparticles and aqueous hydr
- Rajabi, Fatemeh,Naserian, Sareh,Primo, Ana,Luque, Rafael
-
experimental part
p. 2060 - 2066
(2011/10/11)
-
- Silver nitrate catalyzed oxidation of sulfides
-
A variety of sulfides were converted into the corresponding sulfoxide derivatives with 70% tert-butyl hydroperoxide in water as the oxidant in the presence of catalytic quantity of silver nitrate. The method described has a wide range of application, does not involve cumbersome workup, exhibits chemoselectivity, and proceeds under mild reaction conditions, and the resulting products are obtained in good yields within a reasonable time. Georg Thieme Verlag Stuttgart New York.
- Das, Rima,Chakraborty, Debashis
-
experimental part
p. 277 - 280
(2011/03/18)
-
- Transition-metal-free, chemoselective aerobic oxidations of sulfides and alcohols with potassium nitrate and pyridinium tribromide or bromine
-
An efficient oxidation of sulfides with air catalyzed by the combination of potassium nitrate with pyridinium tribromide under transition-metal-free conditions was reported. By replacing pyridinium tribromide with bromine, the reaction system was also useful in the oxidation of alcohols. All reactions afforded the corresponding products in good to excellent yields with high chemoselectivities. Georg Thieme Verlag Stuttgart New York.
- Yuan, Yu,Shi, Xiao,Liu, Wei
-
experimental part
p. 559 - 564
(2011/04/22)
-
- Practical and highly stereoselective method for the preparation of several chiral arylsulfinamides and arylsulfinates based on the spontaneous crystallization of diastereomerically pure N-benzyl-N-(1-phenylethyl)- arylsulfinamides
-
A novel and simple process for the preparation of enantiomerically pure (SS)-benzenesulfinamide (SS)-3a, (SS)-p- toluenesulfinamide (SS)-3b, (SS)-p-chloro- benzenesulfinamide (SS)-3c and (SS)-p- fluorobenzenesulfinamide (SS)-3d has been developed. The treatment of arylsulfinyl chlorides with (R)-N-benzyl-1-phenylethanamine in the presence of excess triethylamine gave diastereomeric mixtures of N-benzyl-N-(1-phenylethyl)- arylsulfinamides 1, which underwent spontaneous crystallization to furnish diastereomerically pure (R,SS)-N-benzyl-N-(1-phenylethyl)- arylsulfinamides (R,SS)-1a-1d in 28%, 29%, 27% and 31% yields, respectively. The diastereomerically pure compounds (R,SS)-1 were then converted into four enantiopure (RS)-methyl arylsulfinates (RS)-2, and finally into four enantiopure (SS)- arylsulfinamides (SS)-3 in good yields.
- Zhu, Rui-Heng,Shi, Xiao-Xin
-
experimental part
p. 387 - 393
(2011/06/11)
-
- TiO2 nanoparticles and Preyssler-type heteropoly acid modified nano-sized TiO2: A facile and efficient catalyst for the selective oxidation of sulfides to sulfones and sulfoxides
-
A new and efficient synthetic method has been developed for the selective conversion of sulfides into their corresponding sulfones and sulfoxides using H2O2 in the presence of neat or Preyssler-type heteropoly acid modified nano-sized TiO2 as catalyst, respectively. The reaction was performed at room temperature with quantitative yields. The catalyst is reusable without significant loss of activity for the next oxidation reaction.
- Rahimizadeh, Mohammad,Rajabzadeh, Ghadir,Khatami, Seyed-Mola,Eshghi, Hossein,Shiri, Ali
-
scheme or table
p. 59 - 64
(2010/09/04)
-
- Cu(II)-catalyzed oxidation of sulfides
-
A variety of sulfides and disulfides were converted into the corresponding sulfoxide derivatives with 70% t-BuOOH (water) as the oxidant in the presence of catalytic quantity of CuBr2. The method described does not involve cumbersome work-up, has wide range of applicabilities, exhibits chemoselectivity, and proceeds under mild reaction conditions, and the resulting products are obtained in good yields within reasonable time.
- Das, Rima,Chakraborty, Debashis
-
scheme or table
p. 6255 - 6258
(2011/01/04)
-