cas 934-72-5, 1-METHYL-4-(METHYLSULFINYL)BENZENE

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Unexpected nucleophilic participation and rearrangement of DBU in reactions with saccharin derivatives
DBU attacks saccharin derivatives with subsequent rearrangement to give rise to 3-[3′-(1″-azepin-2″-onyl)propylamino]-1, 2-benzisothiazole-1,1-dioxide 2 after work-up.
Bulman Page, Philip C.,Vahedi, Hooshang,Bethell, Donald,Barkley, James V.
p. 1937 - 1941
(2003)
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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)

Niobium(V) oxido tris-carbamate as easily available and robust catalytic precursor for the selective sulfide to sulfone oxidation
The oxidation of the sulfide function promoted by a variety of vanadium compounds has been largely explored, whereas the use of homogeneous catalytic systems based on the heavier group 5 metals remains less explored. We report the use of easily available niobium and tantalum carbamates, i.e. [M(O2CNMe2)5] (M = Nb, 1; M = Ta, 2), [Nb(O2CNMe2)4], 3, [NbO(O2CNEt2)3], 4, and [NbCl3(O2CNEt2)2], 5, as effective catalysts for the conversion of a series of alkyl aryl and aromatic sulfides into the corresponding sulfones. NMR investigations on the performant niobium catalyst 4 unexpectedly revealed the substantial stability of this compound in the protic catalytic environment, and a plausible catalytic cycle was obtained by DFT studies. The two active catalytic species, i.e. 4 and its minor mono-methoxide derivative, presumably interconvert to each other exploiting the versatile coordination of the carbamato ligand.
Bresciani, Giulio,Ciancaleoni, Gianluca,Crucianelli, Marcello,Gemmiti, Mario,Marchetti, Fabio,Pampaloni, Guido
(2021/11/01)

Synthesis of a light-harvesting ruthenium porphyrin complex substituted with BODIPY units. Implications for visible light-promoted catalytic oxidations
A light-harvesting ruthenium porphyrin substituted covalently with four boron-dipyrrin (BODIPY) moieties has been synthesized and studied. The resulting complex showed an efficient decarbonylation reaction predominantly due to a photo-induced energy transfer process. Chemical oxidation of the ruthenium(ii) BODIPY-porphyrin afforded a high-energytrans-dioxoruthenium(vi) species that is one order of magnitude more reactive towards alkene oxidation than those analogues supported by conventional porphyrins. In the presence of visible light, the ruthenium(ii) BODIPY-porphyrin displayed remarkable catalytic activity toward sulfide oxidation and alkene epoxidation using iodobenzene diacetate [PhI(OAc)2] and 2,6-dichloropyridineN-oxide (Cl2pyNO) as terminal oxidants, respectively. The findings in this work highlight that porphyrin-BODIPY conjugated metal complexes are potentially useful for visible light-promoted catalytic oxidations.
Malone, Jonathan,Klaine, Seth,Alcantar, Christian,Bratcher, Fox,Zhang, Rui
p. 4977 - 4985
(2021/03/26)

Air atmospheric photocatalytic oxidation by ultrathin C,N-TiO2nanosheets
Herein, we demonstrate the highly efficient photocatalytic sulfide oxidation reaction under mild conditions,i.e.in air, at room temperature and in the absence of a sacrificial reagent, co-catalyst or redox mediator, by using ultrathin C,N-TiO2nanosheets as a photocatalyst.
Cheng, Xiuyan,Zhang, Jianling,Liu, Lifei,Zheng, Lirong,Zhang, Fanyu,Duan, Ran,Sha, Yufei,Su, Zhuizhui,Xie, Fei
supporting information
p. 1165 - 1170
(2021/02/26)

Organocatalytic sulfoxidation
Treatment of a sulfide with a catalytic amount of a 1,3-diketone in the presence of silica sulfuric acid as a co-catalyst and hydrogen peroxide (50% aq) as the stoichiometric oxidant leads to the corresponding sulfoxide product. The reaction is effective for diaryl, aryl-alkyl and dialkyl sulfides and is tolerant of oxidisable and acid sensitive functional groups. Investigations have shown that the tris-peroxide 2, formed on reaction of pentane-2,4-dione with hydrogen peroxide under acidic reaction conditions, can oxidise two equivalents of sulfide using the exocyclic peroxide groups whereas the endocyclic peroxide remains intact. Calculations provide a mechanism consistent with experimental observations and suggest the reaction proceeds via an initial acid catalysed ring opening of a protonated tris-peroxide prior to oxygen transfer to a sulfur nucleophile.
Davidson, Stuart C.,Gomes, Gabriel dos Passos,Kuhn, Leah R.,Alabugin, Igor V.,Kennedy, Alan R.,Tomkinson, Nicholas C.O.
(2020/12/07)

Luminescent cis-Bis(bipyridyl)ruthenium(II) Complexes with 1,2-Azolylamidino Ligands: Photophysical, Electrochemical Studies, and Photocatalytic Oxidation of Thioethers
New 1,2-azolylamidino complexes cis-[Ru(bipy)2(NH=C(R)az*-κ2N,N)](OTf)2 (R = Me, Ph; az? = pz, indz, dmpz) are synthesized via chloride abstraction after a subsequent base-catalyzed coupling of a nitrile with the previously coordinated 1,2-azole. The synt
Cuéllar, Elena,Diez-Varga, Alberto,Torroba, Tomás,Domingo-Legarda, Pablo,Alemán, José,Cabrera, Silvia,Martín-Alvarez, Jose M.,Miguel, Daniel,Villafa?e, Fernando
supporting information
p. 7008 - 7022
(2021/05/29)

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)

Selectivity switch in the aerobic oxygenation of sulfides photocatalysed by visible-light-responsive decavanadate
Nanometre-sized metal oxides are promising species for the development of visible-light-responsive photocatalysts for the selective transformation of organic functional groups. In this article, we report that decavanadate ([V10O28]6-, V10) behaved as an efficient visible-light-responsive photocatalyst in the product-selective oxygenation of sulfides achieved using O2 (1 atm) as the green oxidant. In particular, we revealed that visible-light-responsive photocatalysis of V10 showed remarkable activity for the oxygenation of structurally diverse sulfides to form the corresponding sulfones using O2 in methyl ethyl ketone (MEK). Furthermore, by simply adding water to the reaction mixture, the product selectivity of sulfide oxygenation can be significantly switched toward the production of sulfoxides, without concomitant loss of photocatalytic activity. Based on experimental evidence, we inferred the following mechanistic steps for this photocatalytic system: the aerobic oxygenation of sulfides to form the corresponding sulfoxides initiated by a visible-light-induced photoredox reaction of V10. As for the formation of sulfones, MEK-derived peroxide species as the co-catalysts are probably involved in the oxygenation of sulfoxides to sulfones. The selectivity switch of the V10-photocatalysed reaction brought about by water addition is most likely achieved by suppressing the formation of MEK-derived peroxide species. This journal is
Li, Chifeng,Mizuno, Noritaka,Murata, Kei,Ishii, Kazuyuki,Suenobu, Tomoyoshi,Yamaguchi, Kazuya,Suzuki, Kosuke
supporting information
p. 3896 - 3905
(2020/07/09)

Formation and kinetic studies of manganese(IV)-oxo porphyrins: Oxygen atom transfer mechanism of sulfide oxidations
Visible light irradiation of photo-labile porphyrin-manganese(III) chlorates or bromates (2) produced manganese(IV)-oxo porphyrins [MnIV(Por)(O)] (Por = porphyrin) (3) in three porphyrin ligands. The same oxo species 3 were also formed by chemical oxidation of the corresponding manganese(III) precursors (1) with iodobenzene diacetate, i.e. PhI(OAc)2. The systems under study include 5,10,15,20-tetra(pentafluorophenyl)porphyrin?manganese(IV)-oxo (3a), 5,10,15,20-tetra(2,6-difluorophenyl)porphyrin?manganese(IV)-oxo (3b), and 5,10,15,20-tetramesitylporphyrin?manganese(IV)-oxo (3c). As expected, complexes 3 reacted with thioanisoles to produce the corresponding sulfoxides and over-oxidized sulfones. The kinetics of oxygen atom transfer (OAT) reactions of these generated 3 with aryl sulfides were studied in CH3CN solutions. Second-order rate constants for sulfide oxidation reactions are comparable to those of alkene epoxidations and activated C[sbnd]H bond oxidations by the same oxo species 3. For a given substrate, the reactivity order for the manganese(IV)-oxo species was 3a > 3b > 3c, consistent with expectations on the basis of the electron-withdrawing capacity of the porphyrin macrocycles. Free-energy Hammett analyses gave near-linear correlations with σ values, indicating no significant positive charge developed at the sulfur during the oxidation process. The mechanistic results strongly suggest [MnIV(Por)(O)] reacts as a direct OAT agent towards sulfide substrates through a manganese(II) intermediate that was detected in this work. However, an alternative pathway that involves a disproportionation of 3 to form a higher oxidized manganese(V)-oxo species may be significant when less reactive substrates are present. The competition product studies with the Hammett correlation plot confirmed that the observed manganese(IV)-oxo species is not the true oxidant for the sulfide oxidations catalyzed by manganese(III) porphyrins with PhI(OAc)2.
Klaine, Seth,Bratcher, Fox,Winchester, Charles M.,Zhang, Rui
(2020/01/08)

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)

Iridium complex-linked porous organic polymers for recyclable, broad-scope photocatalysis of organic transformations
Two rigid porous organic polymers (Ir-POP-1 and Ir-POP-2) were prepared from the coupling reactions of tetraphenylmethane tetraborate and two [Ir(ppy)2(dtbbpy)]+-based bitopic linkers and applied as heterogeneous visible-light photocatalysts for organic transformations. Ir-POP-2 was found to exhibit high catalytic activity for a wide range of organic reactions, which include Smiles-Truce rearrangement of alkyliodides, desulfurative conjugate addition to Michael acceptors, and aerobic oxidations of sulfides and arylboronic acids. For all the transformations, Ir-POP-2 could achieve heterogeneous photocatalytic efficiency that rivals that of the homogeneous prototype iridium complexes. This remarkably high photocatalytic performance has been attributed to the large pore size of the conjugated backbone. The new heterogeneous photocatalyst was also highly stable to achieve good recyclability for all the studied reactions and could be reused eight to nineteen times.
Xu, Zi-Yue,Luo, Yi,Zhang, Dan-Wei,Wang, Hui,Sun, Xing-Wen,Li, Zhan-Ting
supporting information
p. 136 - 143
(2020/01/21)

Visible light generation of chromium(V)-oxo salen complexes and mechanistic insights into catalytic sulfide oxidation
Visible light irradiation of the photo-labile salen-chromium(III) chlorate or bromate precursors produced salen-chromium(V)-oxo complexes that were spectroscopically and kinetically indistinguishable from those formed by chemical oxidation of chromium(III) salens with PhI(OAc)2. The photochemistry observed in this work is ascribed to the heterolytic cleavage of the O-X bond in the apical counterion that results in a two-electron oxidation of the metal to form the chromium(V)-oxo species. Second-order rate constants for oxidation reactions of 3 with organic substrates were determined under pseudo-first order condition, and particularly low level of reactivity for sulfide oxidations was observed. In this study, chromium(III) salen complexes effectively catalyzed the oxidation of aryl sulfides into sulfoxides with PhI(OAc)2 in the presence of a small amount of water. The competition product studies with the Hammett correlation plot indicated that the observed chromium(V)-oxo species is not likely to serve as the major oxidant for the sulfide oxidations catalyzed by chromium(III) salens with PhI(OAc)2.
Dames, Angeline,Fung Lee, Ngo,Klaine, Seth,Zhang, Rui
(2020/04/27)

Accurate Regulating of Visible-Light Absorption in Polyoxotitanate-Calix[8]arene Systems by Ligand Modification
With use of a macrocyclic polyphenol, tert-butylcalix[8]arene (TBC[8]), as ligands, a series of TBC[8]-stabilized {Ti4O2}clusters, containing penta- and hexacoordinated Ti centers, were synthesized. Such complexes are "core-shell" shaped containing a {Ti4O2} core arranged in a zigzag fashion. While outer walls of the clusters are decorated by deprotonated TBC[8], their upper and lower surfaces can be modified by various O- or N-donor ligands, and the ratio of the penta- and hexacoordinated Ti(IV) centers in the {Ti4O2} core can be precisely regulated from 4:0, to 3:1, to 2:2, to 1:3, and finally to 0:4. The combined coordination of different ligands in the axial direction shows significant influence on the adsorption of the TBC[8]-Ti4 system in the visible-light region, and their absorption edge can be precisely regulated from 600 to 700 nm. The above structural functionalization in the TBC[8]-Ti4 system also tunes their photocatalytic H2 production activities and oxidative desulfurization ability. Thus, for the first time, by confining the polyoxotitanium cluster in macrocyclic molecules, we provide an example of understanding the structure-property relationship of titanium-oxygen materials by ligand modification.
Liu, Chao,Yang, Xin-Xue,Yi, Xiao-Yi,Yu, Wei-Dong
(2020/06/08)

Hybrid catalysts of molybdovanadophosphoric acid and g-C3N4with tunable bandgaps
The integration of semiconductors and polyoxometalates provides promising benefits for the rational tuning of hybrid materials' electronic band structures; however, the intrinsic influence of certain hybridization approaches on the resulting bandgaps of their complexes has seldom been noted. Herein, graphitic carbon nitride and a series of phosphovanadomolybdates (H3+xPMo12-xVxO40, x = 0-3) have been complexed through electrostatic charge attraction, and their optical and electronic properties are fully explored to investigate the effect of minor variations of the polyoxometalate structures on the hybrid bandgaps and electronic structures. The conduction band edge of the hybrids increases along with the expansion of the number of vanadium centers in the phosphovanadomolybdate, providing potential guidance for the design of hybrid catalysts. This journal is
Cai, Linkun,Hu, Jie,Li, Mu,Yin, Panchao
supporting information
p. 10724 - 10728
(2020/09/02)

Preparation method and application of metal organic cage compound
The invention belongs to the technical field of fine chemical engineering, and relates to a preparation method and application of a metal organic cage compound. According to the preparation method, Zn in transition metal salt is used as a node, L is u
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Paragraph 0037-0040

(2020/08/09)

Synthesis and characterization of VO–vanillin complex immobilized on MCM-41 and its facile catalytic application in the sulfoxidation reaction, and synthesis of 2,3-dihydroquinazolin-4(1H)-ones and disulfides in green media
In this work, a vanillin complex is immobilized onto MCM-41 and characterized by FT-IR, X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis, and BET techniques. This supported Schiff base complex was found to be an efficient and recoverable catalyst for the chemoselective oxidation of sulfides into sulfoxides and thiols into their corresponding disulfides (using hydrogen peroxide as a green oxidant) and also a suitable catalyst for the preparation of 2,3-dihydroquinazolin-4(1H)-one derivatives in water at 90°C. Using this protocol, we show that a variety of disulfides, sulfoxides, and 2,3-dihydroquinazolin-4(1H)-one derivatives can be synthesized in green conditions. The catalyst can be recovered and recycled for further reactions without appreciable loss of catalytic performance.
Nikoorazm, Mohsen,Khanmoradi, Maryam
p. 1477 - 1489
(2020/03/11)

Photocatalytic water-soluble cationic platinum(II) complexes bearing quinolinate and phosphine ligands
Cationic Pt(II) complexes ([Pt(QO/S)(PΛP)]X), having 8-oxy or 8-thioquinolinate (QO/S) and seven different mono- or bidentate phosphines as ligands, have been synthesized and characterized. The photophysical, stability, and photocatalytic properties of th
Alemán, José,Cabrera, Silvia,Casado-Sánchez, Antonio,Domingo-Legarda, Pablo,Marzo, Leyre
p. 13845 - 13857
(2020/11/02)

Catalytic O2activation with synthetic models of α-ketoglutarate dependent oxygenases
An iron complex bearing the facially capping tridentate 1,4,7-triazacyclononane ligand mimics structural and functional features of alpha-ketoglutarate (α-KG) dependent enzymes, and engages in enzyme-like catalytic O2 activation coupled to α-ketoacid decarboxylation, oxygenating sulfides. This system constitutes a rare case of non-enzymatic catalytic O2 activation, cycling between FeII and FeIV(O).
Sánchez-Eguía, Brenda N.,Serrano-Plana, Joan,Company, Anna,Costas, Miquel
supporting information
p. 14369 - 14372
(2020/12/01)

Improved catalytic performance of Co-MOF-74 by nanostructure construction
Herein, we demonstrate for the first time the construction of hollow structural Co-MOF-74, whose shell is as thin as ～50 nm and assembled by nanoparticles ranging from 8 to 18 nm. It exhibits high performance for the photocatalytic oxidation of thioanisole and thermocatalytic cyanosilylation of aldehydes.
Cheng, Xiuyan,Han, Buxing,Wan, Qiang,Zhang, Bingxing,Zhang, Fanyu,Zhang, Jianling,Zhang, Jing,Zheng, Lirong
supporting information
p. 5995 - 6000
(2020/10/18)

Ionic Liquid Stabilized Niobium Oxoclusters Catalyzing Oxidation of Sulfides with Exceptional Activity
We present here a new class of niobium oxoclusters that are stabilized effectively by carboxylate ionic liquids. These functionalized ILs are designated as [TBA][LA], [TBA][PA], and [TBA][HPA] in this work, in which TBA represents tetrabutylammonium and LA, PA, and HPA refer to lactate, propionate, 3-hydroxypropionate anions, respectively. The as-synthesized Nb oxoclusters have been characterized by use of elemental analysis, NMR, IR, XRD, TGA, HRTEM. It was found that [TBA][LA]-stabilized Nb oxoclusters (Nb?OC@[TBA][LA]) are uniformly dispersed with an average particle size of 2–3 nm and afforded exceptionally high catalytic activity for the selective oxidation of various thioethers. The turnover number with Nb?OC@[TBA][LA] catalyst was over 56 000 at catalyst loading as low as 0.0033 mol % (1 ppm). Meantime, the catalyst also showed the high activity for the epoxidation of olefins and allylic alcohols by using only 0.065 mol % of catalyst (50 ppm). The characterization of 93Nb NMR spectra revealed that the Nb oxoclusters underwent structural transformation in the presence of H2O2 but regenerated to their initial state at the end of the reaction. In particular, the highly dispersed Nb oxoclusters can absorb a large amount of polar organic solvents and thus were swollen greatly, which exhibited “pseudo” liquid phase behavior, and enabled the substrate molecules to be highly accessible to the catalytic center of Nb oxocluster units.
Zhou, Qingqing,Ye, Man,Ma, Wenbao,Li, Difan,Ding, Bingjie,Chen, Manyu,Yao, Yefeng,Gong, Xueqing,Hou, Zhenshan
p. 4206 - 4217
(2019/03/26)

Efficient Liquid-Assisted Grinding Selective Aqueous Oxidation of Sulfides Using Supported Heteropolyacid Catalysts
The present work reports the preparation of 40MoAl200 and its full characterization using a number of analytical techniques (XRD, TEM, TGA, BET, EDX). Liquid-assisted ball milling proved to be a key tool to achieve both the best efficiency of 40MoAl200 as a novel Keggin type catalyst in the selective sulfoxidation reaction and also for succeeding in its effective recovery and reuse. In addition, the liquid assisted grinding process was studied in detail evaluating the influence of different parameters such as frequency of rotation (rpm), number and size of the stainless steel balls used and reaction time. The use of aqueous hydrogen peroxide is essential as water proved to exert a crucial role to improve both yields and selectivity towards sulfoxide formation. The procedure was representatively extended to a number of substrates with the possibility to extend the scope of the system to produce sulfoxides in high yields (up to 95 %) and satisfactory selectivities (up to 80 %). The catalyst proved to be recoverable and reusable under the optimized reaction conditions.
Trombettoni, Valeria,Franco, Ana,Sathicq, A. Gabriel,Len, Christophe,Romanelli, Gustavo P.,Vaccaro, Luigi,Luque, Rafael
p. 2537 - 2545
(2019/04/30)

Discovery of a New Family of Polyoxometalate-Based Hybrids with Improved Catalytic Performances for Selective Sulfoxidation: The Synergy between Classic Heptamolybdate Anions and Complex Cations
A series of functional cation-regulated isopolymolybdate-based organic-inorganic hybrid compounds, Na2H2[Mo4O12(C8H17O5N)2]·10H2O (1), Na2[M(Bis-tris)(H2O)]2[Mo7O24]·10H2O [M = Cu, 2; Ni, 3; Co, 4; Zn, 5; Bis-tris = 2,2-Bis(hydroxymethyl)-2,2′,2″-nitrilotriethanol], and (NH4)2[M(Bis-tris)(H2O)]2[Mo7O24]·6H2O (M = Zn, 6; Cu, 7), were synthesized and characterized toward advanced molecular catalyst design. Compound 1 is a covalently bonded adduct, and its self-assembly process can be probed by electrospray ionization mass spectrometry (ESI-MS). Compounds 2-7 are polyoxometalate (POM)-based hybrids containing classic heptamolybdate anions and complex cations with Bis-tris ligands. All of these compounds showed remarkable catalytic effects for selective sulfide oxidation. To the best of our knowledge, compound 5 presents the best catalytic activity so far among the reported hybrid materials with common easily synthesized small-molecule POM clusters and also exhibits outstanding reliability. The conclusion of the catalytic effect is drawn from the results that Zn-based compounds have better catalytic effects than other transition-metal-containing compounds and the compound constructed by Na+ has higher catalytic activity than that constructed by NH4 +. The mechanism studies show that the improvements of the catalytic performance are caused by the synergy between classic heptamolybdate anions and complex cations. ESI-MS data and UV-vis spectra revealed that the POM anions can form intermediate peroxomolybdenum units during catalytic reaction. Further, the combination of the substrate thioanisole with complex cations was characterized by NMR experiments and UV-vis spectra. Thus, a new synergistic mechanism of anions and cations is proposed in which the activated thioanisole is used as a nucleophile to attack the peroxomolybdenum bonds, and this provides a new strategy in the design of reliable POM-based catalysts.
Zhang, Yin,Yu, Wei-Dong,Li, Bin,Chen, Zheng-Fan,Yan, Jun
supporting information
p. 14876 - 14884
(2019/11/05)

A versatile and recyclable molecularly imprinted polymer as an oxidative catalyst of sulfur derivatives: A new possible method for mustard gas and v nerve agent decontamination
A molecularly imprinted polymer containing a porphyrin unit was developed as a biomimetic heterogenous catalyst for the oxidation of sulfur derivatives. Its catalytic efficiency under mild conditions and its easy recovery represent a great asset for the design of new decontamination tools for yperite and VX.
Mohamed, Sophie,Balieu, Sébastien,Petit, Emilie,Galas, Ludovic,Schapman, Damien,Hardouin, Julie,Baati, Rachid,Estour, Fran?ois
supporting information
p. 13243 - 13246
(2019/11/16)

Kinetic and mechanistic aspects of solid state, nanostructured porphyrin diacid photosensitizers in photooxidation of sulfides
In continuation of our studies on the photocatalytic performance of porphyrin diacids, the kinetics and mechanisms of the photooxidation of para-substituted phenyl methyl sulfides (para X = H, CH3, OCH3, Cl, and F) catalyzed by a series of meso-tetra(aryl)porphyrins (aryl = phenyl, 2-chlorophenyl, 2-methylphenyl, 4-chlorophenyl, 4-methylphenyl and 4-methoxyphenyl) immobilized on Amberlyst 15 nanostructures (nanoAmb), H2T(2 or 4-X)PP@nanoAmb, are reported. The immobilization of porphyrins on the polymer was confirmed by diffuse reflectance UV-vis spectroscopy and EDX analysis. While little or no catalyst degradation was observed for a reaction time of ca. 3 h, the electron-deficient porphyrins (pseudo-first-order rate constants, kobs = 0.0049-0.012 min-1) showed faster second-order kinetics than the electron-rich ones (kobs = 2.30 × 10-5-9.92 × 10-4 min-1). The order of photocatalytic activity of the porphyrins approximately correlates with the singlet oxygen quantum yield (φΔ) of the photosensitizers. Diffuse reflectance UV-vis spectra of the immobilized porphyrins demonstrated a large red shift of the Soret and Q bands of the porphyrins which was more dominant in the case of H2T(4-OMe)PP. The weak overlap between the emission spectrum of the light source and the absorption spectrum of the latter was used to explain the low photocatalytic activity of H2T(4-OMe)PP@nanoAmb. The observation of a slope (ρ) of -2.80 for the oxidation of methyl phenyl sulfide and para-substituted phenyl methyl sulfides is in accord with the involvement of an electrophilic oxidation mechanism mediated by singlet oxygen species. H2TPP@naoAmb was recovered and reused at least five times without significant loss of the catalytic activity and detectable catalyst degradation, giving a turnover number of 5 × 5000 for five successive reactions. The catalyst was successfully used for large-scale (up to 6.6 mmol of sulfide per batch, in a 1:10000 catalyst-to-sulfide molar ratio) photooxidation of a wide range of sulfides to the corresponding sulfoxide in a water/acetonitrile solvent mixture.
Nasrollahi, Rahele,Heydari-Turkmani, Akram,Zakavi, Saeed
p. 1260 - 1272
(2019/04/17)

Versatile catalysis of “natural extract”: oxidation of sulfides and alcohols and ipso-hydroxylation of arylboronic acids
Abstract: In the present work, we have described the versatile applications of naturally available inexpensive citrous lemon juice as biocatalyst for controlled oxidation of sulfides and alcohols and ipso-hydroxylation of arylboronic acids using 30% H2O2 as a green oxidant. A series of structurally divergent sulfides and benzyl alcohols were oxidized to their corresponding sulfoxides and aldehydes, respectively, with good-to-excellent yields. Similarly, aryl and heteroaryl boronic acids were rapidly, often within minutes, transformed to their corresponding phenols at room temperature. Graphic abstract: [Figure not available: see fulltext.]
Dutta, Apurba,Ali, Abdul Aziz,Sarma, Diganta
p. 2379 - 2388
(2019/06/28)

Imine-Based Covalent Organic Frameworks as Photocatalysts for Metal Free Oxidation Processes under Visible Light Conditions
Photochemistry of extended polyimine COF structures with laminar, spherical and 3D architectures has been examined. We show that these materials, composed by undecorated phenyl rings and imine fragments, can act as photocatalyts in oxidative transformatio
Jiménez-Almarza, Alicia,López-Magano, Alberto,Marzo, Leyre,Cabrera, Silvia,Mas-Ballesté, Rubén,Alemán, José
p. 4916 - 4922
(2019/09/10)

Polymer immobilized tantalum(v)-amino acid complexes as selective and recyclable heterogeneous catalysts for oxidation of olefins and sulfides with aqueous H2O2
Polymer supported heterogeneous peroxotantalum(v) catalysts were prepared by anchoring Ta(v)-diperoxo species to chloromethylated poly(styrene-divinylbenzene) resin functionalized with amino acids asparagine (l-Asn) and arginine (l-Arg). The structurally well-defined catalysts, [Ta(O2)2(L)2]--MR, [L = asparagine (catalyst 1) or arginine (catalyst 2) and MR = Merrifield resin], were comprehensively characterized by elemental analysis (CHN, ICP-OES, energy dispersive X-ray spectroscopy), spectral studies (FT-IR, Raman, 13C NMR, diffuse reflectance UV-vis and XPS), SEM, XRD, Brunauer-Emmett-Teller (BET) and thermogravimetric analysis (TGA). The supported peroxotantalum (pTa) compounds displayed excellent catalytic performance in epoxidation of alkenes with 30% H2O2, under solvent free reaction conditions. Styrene was epoxidized with >99% selectivity with the highest TOF of 1040 h-1 obtained within 30 min reaction time, whereas the TOF for norbornene epoxidation was 2000 h-1 within 1 h with >95% epoxide selectivity. Furthermore, the immobilized catalysts facilitated chemoselective oxidation of a broad range of organic sulfides to the desired sulfoxides with H2O2 in methanol, under mild reaction conditions. The oxidations proceeded with a high H2O2 efficiency percentage and are amenable to ready scalability. The heterogeneous catalysts could be easily recovered and reused for several consecutive catalytic cycles with undiminished activity/selectivity profiles in all cases. The developed catalytic strategies are operationally simple and, being free from halogenated solvent or any other toxic auxiliaries, environmentally clean.
Saikia, Gangutri,Ahmed, Kabirun,Rajkhowa, Chandrasee,Sharma, Mitu,Talukdar, Hiya,Islam, Nashreen S.
p. 17251 - 17266
(2019/11/20)

Water-soluble polymer anchored peroxotitanates as environmentally clean and recyclable catalysts for mild and selective oxidation of sulfides with H2O2 in water
Anchoring of peroxotitanium (pTi) species to linear water-soluble acrylic acid based polymers, poly(sodium acrylate) (PA) and poly(sodium methacrylate) (PMA) led to the successful synthesis of a pair of new, water-tolerant and recyclable catalysts of the type [Ti2(O2)2O2(OH)2]4-—L (L = PA or PMA), highly effective in chemoselective sulfoxidation of organic sulfides with 30% H2O2 in aqueous medium at ambient temperature. The catalytic protocol is high yielding (TOF up to 11,280 h?1), operationally simple as well as environmentally clean and safe, being free from halide, or any other toxic auxiliaries. The catalysts are sufficiently stable to afford easy recyclability for at least 10 consecutive reaction cycles of sulfoxidation with consistent activity selectivity profile. Oxidation of dibenzothiophene (DBT) to respective high purity sulfoxide or sulfone could also be accomplished using the same catalysts by variation of reaction conditions.
Ahmed, Kabirun,Saikia, Gangutri,Paul, Sivangi,Baruah, Satyajit Dey,Talukdar, Hiya,Sharma, Mitu,Islam, Nashreen S.
(2019/10/02)

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)

Insights from kinetic studies of photo-generated compound II models: Reactivity toward aryl sulfides
Iron(IV)-oxo porphyrins [FeIV(Por)O] (Por = poprhyrin), commonly called compound II models, were produced in three electron-deficient ligands by visible light irradiation of highly photo-labile porphyrin-iron(III) bromates or chlorates. The kinetics of oxygen transfer atom (OAT) reactions with aryl sulfides by these photo-generated [FeIV(Por)O] (3) were studied in CH3CN solutions. The iron(IV)-oxo porphyrins under study include 5,10,15,20-tetra(2,6-dichlorophenyl)porphyrin-iron(IV)-oxo (3a), 5,10,15,20-tetra(2,6-difluorophenyl)porphyrin-iron(IV)-oxo (3b), and 5,10,15,20-tetra(pentafluorophenyl)porphyrin-iron(IV)-oxo (3c). As expected, complexes 3 were competent oxidants and reacted rapidly with thioanisoles to give the corresponding sulfoxides with minor over-oxidation sulfones. Apparent second-order rate constants determined under pseudo-first-order conditions for sulfide oxidation reactions are (9.8 ± 0.1) × 102–(3.7 ± 0.3) × 101 M?1 s?1, which are 3 to 4 orders of magnitude greater in comparison to those of alkene epoxidations and activated C–H bond oxidations by the same oxo species. Conventional Hammett analyses gave non-linear correlations, indicating no significant charge developed at the sulfur during the oxidation process. For a given substrate, the reactivity order for the iron(IV)-oxo species was 3c 3b 3a, which is inverted from expectations on the basis of the electron-withdrawing capacity of the porphyrin macrocycles. The absolute rate constants from kinetic studies provided insights into the transient oxidants in catalytic reactions under turnover conditions where actual reactive intermediates are not observable. Our kinetic and catalytic competition results strongly suggest that 3 may undergo a disproportionation reaction to form a higher oxidized iron(IV)-oxo porphyrin radical cations as the true oxidant.
Lee, Ngo Fung,Patel, Dharmesh,Liu, Haiyan,Zhang, Rui
p. 58 - 65
(2018/03/21)

An isotetramolybdate-supported rhenium carbonyl derivative: Synthesis, characterization, and use as a catalyst for sulfoxidation
A novel isotetramolybdate-supported rhenium carbonyl derivative, [(CH3)4N]4[{Re(CO)3}4(Mo4O16)]·H2O (1), has been successfully synthesized and characterized by single crystal X-ray diffraction crystallography, IR and UV spectroscopy, etc. Results showed that, compound 1 is an efficient catalyst for the oxidation of thioanisole into the corresponding sulfoxide in the presence of hydrogen peroxide with good to excellent conversion (99%) and excellent selectivity (93%). Highly efficient oxygenation of thioanisole can also be achieved with 100% selectivity of sulfone and >99% conversion. Furthermore, optimized conditions were applied to a range of sulfides to obtain the corresponding sulfoxides and sulfones.
Lu, Jingkun,Ma, Xinyi,Singh, Vikram,Zhang, Yujiao,Ma, Pengtao,Zhang, Chao,Niu, Jingyang,Wang, Jingping
p. 5279 - 5285
(2018/04/23)

Polyoxometalate LUMO engineering: A strategy for visible-light-responsive aerobic oxygenation photocatalysts
We report the efficient visible-light-responsive photocatalysis of polyoxometalates (POMs) by engineering the lowest unoccupied molecular orbitals (LUMOs). By the introduction of vanadium atoms into the γ-Keggin-type phosphotungstate, a new V3d/W5d mixed LUMO appeared to afford a visible-light-responsive catalyst (I), which showed high photocatalytic activity for aerobic oxygenation of sulfides to sulfoxides.
Li, Chifeng,Suzuki, Kosuke,Mizuno, Noritaka,Yamaguchi, Kazuya
supporting information
p. 7127 - 7130
(2018/07/05)

A multifunctional Co-based metal-organic framework: heterogeneous catalysis, chemiluminescence sensing and moisture-dependent solvatochromism
Crystalline materials with multi-catalytic applications are of great value to both fundamental research and practical applications. The platform of metal-organic frameworks (MOFs) is utilized to fabricate a microporous versatile catalyst with high stability. Self-assembly of a flexible ligand, 4-(4-carboxybenzylamino)benzoic acid (H2CBBA), with Co(ii) resulted in a 3D framework, CBBA-Co, with Co3O clusters exposed in the zigzag channels. Upon in situ activation, CBBA-Co exhibited multiple heterogeneous catalytic activities. Theoretical calculations were carried out to give insights into the catalytic process. In addition, CBBA-Co also showed promising potential in optical sensing by virtue of its catalytic activity. The luminol chemiluminescence was greatly enhanced by CBBA-Co, and linear determination of the concentration of H2O2 in the range of 0-30% was established. The successful implementation of CBBA-Co indicates the feasibility and promising future of employing MOFs as an efficient platform for the fabrication and study of multifunctional catalysts, both experimentally and theoretically.
Xie, Ming-Hua,Wang, Ya,Li, Ruo-Fei,Dong, Peng-Yu,Hou, Gui-Hua,Shao, Rong,Xi, Xin-Guo,Guan, Rong-Feng,Yang, Xiu-Li
p. 12406 - 12413
(2018/09/25)

Optically active polyoxometalate-based silica nanohelices: Induced chirality from inorganic nanohelices to achiral POM clusters
In order to investigate the principle of chiral induction from nanometric silica helices to polyoxometalate (POM) clusters, a series of optically active silica POM-based nanohelices (NANOPOMs) have been prepared by electrostatic grafting and direct adsorption of a-Keggin polyoxometalate [a-PW12 O40]3 to well-defined left-and right-handed silica nanohelices. UV/Vis, Raman, DRIFT, TEM, HR-TEM, EDS and circular dichroism (CD) spectroscopy were used to characterize these NANOPOMs, and confirm the presence of POM clusters as well as their interactions with the helical support. The optical activity of the left-handed and right-handed NANOPOMs has been proven by CD spectroscopy. Their CD spectra are mirror images of one another, showing cotton effects at around 214 and 276 nm, this last contribution corresponding to the oxygen-to-tungsten charge-transfer bands of Keggin polyoxoanions. The CD signal of POM clusters is strongly enhanced for NANOPOMs built by adsorption of POM onto silica nanohelices, indicating a better induced optical activity to POM clusters. These nanohelices are stable, recoverable and active catalysts in the oxidation of sulfides. To the best of our knowledge, the present research represents the first examples of optically active POM-containing silica nanohelices in which achiral POM clusters have been grafted onto silica nanohelices, and display chiroptical effects.
Attoui, Mariam,Pouget, Emilie,Oda, Reiko,Talaga, David,Bourdon, Gwéna Lle Le,Buffeteau, Thierry,Nlate, Sylvain
p. 11344 - 11353
(2018/10/20)

Schiff base Mn(III) and Co(II) complexes coated on Co nanoparticles: An efficient and recyclable magnetic nanocatalyst for H2O2 oxidation of sulfides to sulfoxides
In this paper, an effective and selective heterogeneous catalyst was produced by immobilization of manganese and cobalt Schiff base-complexes on Co magnetite nanoparticles (MNP). The catalysts Co@SiO2[(EtO)3Si-L3]/M (M = Mn(iii) and Co(ii)) were synthesized using Co@SiO2 core-shell nanoparticles and amino-functionalized Co@SiO2. The Schiff base ligand Co@SiO2[(EtO)3Si-L3] was synthesized by reacting Co@SiO2 core-shell nanoparticles with 2-hydroxy 1-naphthaldehyde for the synthesis of Co@SiO2[(EtO)3Si-L3]/M. The catalysts were characterized by several techniques, such as FT-IR, TEM, XRD, TGA and VSM. The catalytic activities of the prepared catalysts were studied by oxidation of sulfides to the sulfoxides under different conditions. These catalysts can be easily recovered and reused in at least seven sequential cycles without considerable leaching and loss of reactivity.
Saremi, Shokoufeh Ghahri,Keypour, Hassan,Noroozi, Mohammad,Veisi, Hojat
p. 3889 - 3898
(2018/02/07)

A novel catalytic system poly(1-vinyl-3-dodecylimidazolium tribromide)/TBN for the oxidation of sulfides to sulfoxides with air as oxidant
A novel and recoverable polymeric ionic liquid, poly(1-vinyl-3-dodecylimidazolium tribromide) (Poly[VDIM]Br3), was successfully prepared and fully characterized. And a highly efficient metal-free catalytic system Poly[VDIM]Br3/tert-butyl nitrite was developed for the oxidation of sulfides. With air as oxidant, we have successfully achieved 19 kinds of sulfides selectively and efficiently oxidized to corresponding sulfoxides using this catalytic system at room temperature.
Zhang, Hua,Qi, Linlin
p. 3171 - 3174
(2018/07/13)

Selective oxidation of sulfides to sulfoxides using novel nano Br?nsted dicationic ionic liquid as effective reagent under grinding conditions
In this work, 1,1′-(butane-1,4-diyl)bis(1,4-diazabicyclo[2.2.2]octane-1,4-diium) bis(hydrogen sulfate) dinitrate ([C4(DABCO-H)2]·[HSO4]2[NO3]2) as a novel Br?nsted dicationic ionic liquid w
Bayat, Yadollah,Shirini, Farhad,Goli-Jolodar, Omid
p. 517 - 524
(2018/06/26)

Carbazole-triazine based donor-acceptor porous organic frameworks for efficient visible-light photocatalytic aerobic oxidation reactions
We report the synthesis of a series of carbazole-triazine based donor-acceptor (D-A) POFs and their photocatalytic activities for aerobic oxidation reactions. The simultaneous introduction of a carbazole-based electron donor and a triazine-based electron acceptor in D-A POFs stabilizes the charge transfer state and enables an efficient triplet-triplet energy transfer to generate 1O2. Meanwhile, systematic variation of the D-A distance results in the tunable photoredox properties and consequently the efficiency for generation of reactive oxygen species (ROSs). Upon visible light excitation, all three D-A POFs exhibit excellent capability to promote three aerobic oxidations: sulfide oxidation, oxidative amine coupling, and Mannich reactions. This systematic study validates the design principle of D-A POFs as high-performance photo-oxidation catalysts with wide substrate scope and excellent stability and recyclability.
Luo, Jian,Lu, Jingzhi,Zhang, Jian
supporting information
p. 15154 - 15161
(2018/08/17)

Systematic Evaluation of Sulfoxides as Catalysts in Nucleophilic Substitutions of Alcohols
Herein, a method for the nucleophilic substitution (SN) of benzyl alcohols yielding chloro alkanes is introduced that relies on aromatic sulfoxides as Lewis base catalysts (down to 1.5 mol-%) and benzoyl chloride (BzCl) as reagent. A systematic screening of various sulfoxides and other sulfinyl containing Lewis bases afforded (2-methoxyphenyl)methyl sulfoxide as optimal catalyst. In contrast to reported formamide catalysts, sulfoxides also enable the application of plain acetyl chloride (AcCl) as reagent. In addition, it was demonstrated that weakly electrophilic carboxylic acid chlorides like BzCl promote Pummerer rearrangement of sulfoxides already at room temperature. This side-reaction also provided the explanation, why sulfoxide catalyzed SN-reactions of alcohols do not allow the effective production of aliphatic and electron deficient chloro alkanes. Comparison experiments provided further insight into the reaction mechanism.
Motsch, Sebastian,Schütz, Christian,Huy, Peter H.
supporting information
p. 4541 - 4547
(2018/09/13)

Chemoenzymatic Deracemization of Chiral Sulfoxides
The highly enantioselective enzyme methionine sulfoxide reductase A was combined with an oxaziridine-type oxidant in a biphasic setup for the deracemization of chiral sulfoxides. Remarkably, high ee values were observed with a wide range of substrates, thus providing a practical route for the synthesis of enantiomerically pure sulfoxides.
Nosek, Vladimír,Mí?ek, Ji?í
supporting information
p. 9849 - 9852
(2018/07/31)

Electrochemical synthesis of methyl sulfoxides from thiophenols/thiols and dimethyl sulfoxide
A new route for a one-pot synthesis of methyl sulfoxides from thiophenols/thiols and dimethyl sulfoxide using an electrochemical technique was developed. This protocol proceeded smoothly by employing electrons and hydrogen peroxide as clean oxidants, and a wide range of aromatic and aliphatic sulfoxides were synthesized in moderate to good yields.
Du, Ke-Si,Huang, Jing-Mei
p. 1405 - 1411
(2018/03/27)

Catalytic Activity of Crystallographically Characterized Organic–Inorganic Hybrid Containing 1,5-Di-amino-pentane Tetrachloro Manganate with Perovskite Type Structure
Abstract: Layered 2D organic–inorganic hybrid perovskite (OIHS) of the diammonium series, 1,5 di-aminepentane tetrachloro mangenate ([NH3–(CH2)5–NH3] MnCl4) was prepared by slow evaporation and reducing temperature method and characterized by single crystal X-ray diffraction analysis. Its structure consists of organic cation, [NH3(CH2)5NH3]+2 extended in a zigzag fashion and inorganic anion, [MnCl6]?2 where Mn2+ is coordinated by six Cl? ion in octahedral fashion. The organic and inorganic segments are alternately stacked along c-axis where inorganic layer is extended through corner-shared octahedra sandwiched by the di-aminopentane molecules. The layers (organic and inorganic) were connected to each other through N–HCl hydrogen bonds and van-der Waals interaction to build cation–anion–cation cohesion. The hybrid crystal had orthorhombic non-centrosymetric system having I212121 space group with unit cell parameters a = 7.1742(3) ?, b = 7.3817(3) ?, c = 23.9650(10) ?, V = 1269.13 ?3 and Z = 4. The hybrid exhibited excellent catalytic activity towards sulphide and alkene oxidation using aqueous H2O2 as an oxidant. Graphical Abstract: OIHS of the diammonium series [NH3–(CH2)5–NH3] MnCl4; 1,5 di-aminepentane tetrachloro mangenate were prepared by slow evaporation and temperature decrease method, characterized by single crystal X-ray diffraction. This complex exhibits excellent catalytic activity towards sulphide oxidation and alkene oxidation using aqueous H2O2 as an oxidant. [Figure not available: see fulltext.].
Mondal, Paramita,Abdel-Aal, Seham Kamal,Das, Debasis,Islam, Sk Manirul
p. 2332 - 2339
(2017/08/22)

The Polyoxovanadate-Based Carboxylate Derivative K6H[VV17VIV12(OH)4O60(OOC(CH2)4COO)8]·nH2O: Synthesis, Crystal Structure, and Catalysis for Oxidation of Sulfides
The high-nuclearity polyoxovanadate-based carboxylate derivative K6H[VV17VIV12(OH)4O60(OOC(CH2)4COO)8]·nH2O (1) has been successfully synthesized by conventional aqueous methods and structurally characterized. The [VV17VIV12(OH)4O60(OOC(CH2)4COO)8]7- polyanion is built up from three cages: one {VV17(OH)4O44} cage and two identical [(VIV3O6)2(OOC(CH2)4COO)4]8- cages. Of the three cages, the {VV17(OH)4O44} is a purely inorganic polyoxovanadate cluster, whereas each of the [(VIV3O6)2(OOC(CH2)4COO)4]8- cages is a vanadium-based organic-inorganic hybrid cluster framed via four adipate ligands linking simultaneously to two triangular {V3} units. The two [(VIV3O6)2(OOC(CH2)4COO)4]8- cages are covalently attached to the central {VV17(OH)4O44} cage via V-O-V bonds in a linear arrangement, resulting in a {V29}-based hybrid cluster skeleton. The catalytic properties of compound 1 for the oxidation of sulfides by tert-butyl hydroperoxide were investigated, and the result indicates that 1 exhibits excellent catalytic activity for the oxidation of sulfides under mild conditions.
Wang, Ke,Niu, Yanjun,Zhao, Dongyan,Zhao, Yanxin,Ma, Pengtao,Zhang, Dongdi,Wang, Jingping,Niu, Jingyang
p. 14053 - 14059
(2017/11/27)

Access to N-cyanosulfoximines by transition metal-free iminations of sulfoxides
A transition metal-free synthesis of N-cyanosulfoximines from sulfoxides using N-chlorosuccinimide (NCS) as oxidising agent and cyanamide as nucleophilic amine source is reported. The products are obtained in moderate to excellent yields. The protocol enables an easy access to N-cyanosulfoximines from readily available starting materials under inversion of configuration at a preexisting stereogenic center.
Dannenberg,Fritze,Krauskopf,Bolm
supporting information
p. 1086 - 1090
(2017/02/10)

Synthesis, Characterization and Catalytic Activity of a Tungsten(VI) Amino Triphenolate Complex
Abstract: Synthesis, characterization and catalytic activity of a novel tungsten(VI) amino triphenolate complex have been investigated. In particular, a tungsten(VI) amino triphenolate complex has been synthesized and tested in the oxidation of sulfides and cyclooctene, using hydrogen peroxide as terminal oxidant. The catalyst has proved to be air and water tolerant, also showing a good efficiency in terms of yields and selectivity. Moreover, an upgrade of our previous ligand synthesis is herein reported. The new developed procedure allows to obtain the triphenolamine in large scale without the use of chromatography for the intermediates purification. Graphical Abstract: [Figure not available: see fulltext.].
Badetti, Elena,Bonetto, Alessandro,Romano, Francesco,Marchiò, Luciano,Zonta, Cristiano,Licini, Giulia
p. 2313 - 2318
(2017/08/22)

1,1,2,2-Tetrahydroperoxy-1,2-diphenylethane as new oxidant for chemoselective and catalyst free oxidation of sulfides to sulfoxides and sulfones
A catalyst free and chemoselective oxidation of sulfides to sulfoxides or sulfones was developed using 1,1,2,2-tetrahydroperoxy-1,2-diphenylethane as a new oxidant. This scope has shown the achievement of various sulfoxides and sulfones which were obtained selectively in high yields at room temperature.
Khosravi, Kaveh,Naserifar, Shirin,Mahmoudi, Boshra,Khalaji, Kobra
p. 316 - 321
(2017/02/18)

Synthesis method of aryl sulfoxide compound
The invention relates to a synthesis method of an aryl sulfoxide compound shown in the following formula (II). The synthesis method comprises the steps as follows: a compound shown in formula (I) is subjected to a catalytic oxidation reaction by using a c
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Paragraph 0050; 0051; 0052; 0053-0055; 0111; 0116; 0121

(2017/07/20)

Direct Irradiaton of Aryl Sulfides: Homolytic Fragmentation and Sensitized S-Oxidation
The direct irradiation of diphenyl sulfide and p-substituted thioanisoles in the presence of oxygen was investigated by means of both steady state and laser flash photolysis experiments. Two competitive pathways took place from the triplet excited state o
Bonesi, Sergio M.,Crespi, Stefano,Merli, Daniele,Manet, Ilse,Albini, Angelo
p. 9054 - 9065
(2017/09/11)

SULFOXIDATION CATALYSTS AND METHODS FOR THEIR PREPARATION AND USE
Methods and compositions of catalysts for sulfoxidation reaction processes are disclosed. The sulfoxidation reaction process can be performed in an aqueous medium, and the catalysts can be recycled for further use. In some embodiments, a method of making a catalyst may include contacting a transition metal compound with an oxidizing agent to form a first solution, contacting a carboxylic acid compound with a cationic surfactant to form a second solution, mixing the first solution and the second solution to form a precipitate, and isolating the precipitate.
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Paragraph 0054; 0055

(2016/09/26)

Manganese- and Lanthanide-Based 1D Chiral Coordination Polymers as an Enantioselective Catalyst for Sulfoxidation
The chiral 1D-coordination polymers (CP) {[Ln2(MnLCl)2(NO3)2(dmf)6(H2O)2]·xH2O}n [Ln = Pr (1), Nd (2), Sm (3), and Gd (4)] were synthesized by the reaction of N,N'-bis(4-carboxysalicylidene)cyclohexanediamine (H4L) with [MnCl2·4(H2O)] and [Ln(NO3)3·x(H2O)] in the presence of dmf/pyridine at 90 °C. The polymers consist of manganese-salen-based moieties having carboxylate linkers connected to rare earth atoms in a 1D-chain structure. The polymers are very easily accessible. A one-step synthesis for the ligand and a second step for the preparation of the 1D coordination polymers starting from commercially available material are needed. The solid state structures of 1-4 were established by single-crystal X-ray diffraction. Compounds 1-4 were investigated as heterogeneous catalysts for the sulfoxidation reaction of various alkyl and aryl sulfides. The influence of various solvents and oxidizing agents on the catalytic reaction was examined. It was found that the catalysts were active for more than one reaction cycle without significant loss of activity. For phenylsulfide with 1 mol % of the catalyst 4, a maximum conversion 100% and a chemoselectivity 88% were observed.
Yadav, Munendra,Bhunia, Asamanjoy,Jana, Salil K.,Roesky, Peter W.
supporting information
p. 2701 - 2708
(2016/04/05)