- Visible-light-promoted aerobic oxidation of sulfides and sulfoxides in ketone solvents
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Simple and readily available ketones have been identified to promote the visible-light-promoted aerobic oxidation of sulfides and sulfoxides to sulfones. We report a simple and environmental-friendly oxidation protocol of sulfides to sulfones. Various sulfides were efficiently oxidized into sulfones with O2 as sustainable terminate oxidant, readily available thioxanthone as the photocatalyst and 3-pentanone (DEK) as the solvent. The protocol tolerates diverse functional groups, including halogens, ketone, ester, cyano, heterocycle and even cyclopropyl groups. The detection of the aerobic oxidation reaction in DEK by GC and HRMS disclosed that the key active intermediates were generated.
- Li, Xiaotong,Wang, Yu,Xie, Xiaomin,Yang, Liqun,Zhang, Zhaoguo
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supporting information
(2022/03/09)
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- Modulating catalytic activity of a modified flavin analogue: Via judicially positioned metal ion toward aerobic sulphoxidation
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This manuscript describes the synthesis, spectroscopic and crystallographic characterization of a cadmium complex of 10-propoylisoalloxazine-7-carboxylic acid (Flc-Cd). Catalytic activity of Flc-Cd towards aerobic sulphoxidation reaction was investigated in the presence of l-ascorbic acid as the reducing agent. Notably the neutral un-metalated flavin analogue did not show any significant catalytic activity. The design strategy for Flc provides a close proximity of the metal centre to the flavin core without compromising the catalytic site thereby assisting the product formation when compared to unmetallated Flc. Minor enantioselectivity is also observed in cases where unsymmetrical sulphides were used; indicative of the possible involvement of chiral l-ascorbic acid in the intermediate formation. This journal is
- Mishra, Ashutosh Kumar,Mouli, M. S. S. Vinod
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p. 3990 - 3995
(2022/02/16)
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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
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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
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supporting information
p. 496 - 500
(2021/01/28)
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- Bidentate Nitrogen-Ligated I(V) Reagents, Bi(N)-HVIs: Preparation, Stability, Structure, and Reactivity
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Hypervalent iodine(V) reagents are a powerful class of organic oxidants. While the use of I(V) compounds Dess-Martin periodinane and IBX is widespread, this reagent class has long been plagued by issues of solubility and stability. Extensive effort has been made for derivatizing these scaffolds to modulate reactivity and physical properties but considerable room for innovation still exists. Herein, we describe the preparation, thermal stability, optimized geometries, and synthetic utility of an emerging class of I(V) reagents, Bi(N)-HVIs, possessing datively bound bidentate nitrogen ligands on the iodine center. Bi(N)-HVIs display favorable safety profiles, improved solubility, and comparable to superior oxidative reactivity relative to common I(V) reagents. The highly modular synthesis and in situ generation of Bi(N)-HVIs provides a novel and convenient screening platform for I(V) reagent and reaction development.
- Xiao, Xiao,Roth, Jessica M.,Greenwood, Nathaniel S.,Velopolcek, Maria K.,Aguirre, Jordan,Jalali, Mona,Ariafard, Alireza,Wengryniuk, Sarah E.
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p. 6566 - 6576
(2021/05/06)
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- Flow Electrosynthesis of Sulfoxides, Sulfones, and Sulfoximines without Supporting Electrolytes
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An efficient electrochemical flow process for the selective oxidation of sulfides to sulfoxides and sulfones and of sulfoxides toN-cyanosulfoximines has been developed. In total, 69 examples of sulfoxides, sulfones, andN-cyanosulfoximines have been synthesized in good to excellent yields and with high current efficiencies. The synthesis was assisted and facilitated through a supporting electrolyte-free, fully automated electrochemical protocol that highlights the advantages of flow electrolysis.
- Amri, Nasser,Wirth, Thomas
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p. 15961 - 15972
(2021/07/20)
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- Modulation of photochemical oxidation of thioethers to sulfoxides or sulfones using an aromatic ketone as the photocatalyst
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We have developed an eco-friendly and chemo-selective photocatalytic synthesis of sulfoxides or sulfones via oxidation of sulfides (thioethers) at ambient temperature using air or O2 as the oxidant. An inexpensive thioxanthone was used as the photocatalyst. Our method offers excellent chemical yields and good functional group tolerance. The hydrogen bonding between hexafluoro-2-propanol (HFIP) and sulfoxides may play an important role in minimizing the over-oxidization of sulfoxides.
- Zhao, Bin,Hammond, Gerald B.,Xu, Bo
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supporting information
(2021/09/13)
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- Lanthanide complexes based on an anthraquinone derivative ligand and applications as photocatalysts for visible-light driving photooxidation reactions
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Four isostructural lanthanide coordination complexes based on 3,7-diamino-9,10-anthraquinone-2,6-disulfonate (dianionic, L) have been synthesized by hydrothermal method, namely [Er(L)(H2O)6]?[Er(H2O)8]?2L?8H2O (Er-L), [Tm(L)(H2O)6]?[Tm(H2O)8]?2L?8.5H2O (Tm-L), [Yb(L)(H2O)6]?[Yb(H2O)8]?2L?9H2O (Yb-L), [Lu(L)(H2O)6]?[Lu(H2O)8]?2L?9H2O (Lu-L). Single-crystal X-ray analysis reveals the existence of both coordinated and free ligand L in the crystal structure. Versatile sulfonate groups on these distinct L ligands, together with very rich coordinated and lattice water molecules, form a lot of hydrogen-bonding motifs that contribute to the stabilization of the crystal packing. It is interesting that the ligands stack into columns through strong π-π interactions and the centroid-centroid distances are between 3.281 and 3.331 ?. These ligands are stacked in an alternate off-set mode to avoid the steric hindrance between the bulky sulfonate groups, generating a repeated structural unit involving six stacked ligands. These lanthanide complexes proved to be good heterogeneous photocatalyst for promoting the visible-light driving photooxidation reactions of diarylacetylenes and thioethers. The Er-L complex exhibited the best catalytic activity and showed good catalytic efficiency over a wide range of substrates for both reaction systems. The Er-L photocatalyst can be easily isolated by simple filtration as crystalline material upon completion of the photooxidation reaction without structure change, and can be recycled for at least five catalytic cycles with persistent catalytic efficiency without any need of activation or regeneration. This family of lanthanide complexes represent a category of promising heterogeneous photocatalysts in terms of green chemistry, with the potential of promoting organic transformations highly efficiently under the irradiation of visible light.
- Zhu, Ting-Ting,Tao, Yu-Tong,Sun, Yue,Wang, Xue,Zhang, Xiao-Wen,Chai, Jia-Lu,Han, Jie,Zhao, Xiao-Li,Chen, Xu-Dong
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- Sulfoxide and Sulfone Synthesis via Electrochemical Oxidation of Sulfides
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The oxidation of diaryl sulfides and aryl alkyl sulfides to the corresponding sulfoxides and sulfones under electrochemical conditions is reported. Sulfoxides are selectively obtained in good yield under a constant current of 5 mA for 10 h in DMF, while sulfones are formed as the major product under a constant current of 10 or 20 mA for 10 h in MeOH. The oxygen of both the sulfoxide and sulfone function is derived from water.
- Lee, Sunwoo,Park, Jin Kyu
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p. 13790 - 13799
(2021/10/12)
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- Catalytic activity of bis p-nitro A2B (oxo)Mn(V) corroles towards oxygen transfer reaction to sulphides
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The 5 A2B Mn(III) corroles have been synthesized, fully characterized and used for oxygen atom transfer (OAT) from isolated (oxo)manganese(V)corrole to sulfide. Oxidation of Mn(III) were carried out using ozone, a clean oxidant, which resulted
- Kumar, Anil,Varshney, Atul,Yadav, Sunil
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- Mechanistic insight into oxygen atom transfer reactions by mononuclear manganese(iv)-oxo adducts
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High-valent metal-oxo intermediates are well known to facilitate oxygen-atom transfer (OAT) reactions both in biological and synthetic systems. These reactions can occur by a single-step OAT mechanism or by a stepwise process initiated by rate-limiting el
- Singh, Priya,Stewart-Jones, Eleanor,Denler, Melissa C.,Jackson, Timothy A.
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supporting information
p. 3577 - 3585
(2021/03/22)
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- The Stereoselective Oxidation of para-Substituted Benzenes by a Cytochrome P450 Biocatalyst
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The serine 244 to aspartate (S244D) variant of the cytochrome P450 enzyme CYP199A4 was used to expand its substrate range beyond benzoic acids. Substrates, in which the carboxylate group of the benzoic acid moiety is replaced were oxidised with high activity by the S244D mutant (product formation rates >60 nmol.(nmol-CYP)?1.min?1) and with total turnover numbers of up to 20,000. Ethyl α-hydroxylation was more rapid than methyl oxidation, styrene epoxidation and S-oxidation. The S244D mutant catalysed the ethyl hydroxylation, epoxidation and sulfoxidation reactions with an excess of one stereoisomer (in some instances up to >98 %). The crystal structure of 4-methoxybenzoic acid-bound CYP199A4 S244D showed that the active site architecture and the substrate orientation were similar to that of the WT enzyme. Overall, this work demonstrates that CYP199A4 can catalyse the stereoselective hydroxylation, epoxidation or sulfoxidation of substituted benzene substrates under mild conditions resulting in more sustainable transformations using this heme monooxygenase enzyme.
- Chao, Rebecca R.,Lau, Ian C.-K.,Coleman, Tom,Churchman, Luke R.,Child, Stella A.,Lee, Joel H. Z.,Bruning, John B.,De Voss, James J.,Bell, Stephen G.
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p. 14765 - 14777
(2021/09/14)
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- Direct structural and mechanistic insights into fast bimolecular chemical reactions in solution through a coupled XAS/UV-Vis multivariate statistical analysis
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In this work, we obtain detailed mechanistic and structural information on bimolecular chemical reactions occurring in solution on the second to millisecond time scales through the combination of a statistical, multivariate and theoretical analysis of time-resolved coupled X-ray Absorption Spectroscopy (XAS) and UV-Vis data. We apply this innovative method to investigate the sulfoxidation of p-cyanothioanisole and p-methoxythioanisole by the nonheme FeIV oxo complex [N4Py·FeIV(O)]2+ (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) in acetonitrile at room temperature. By employing statistical and multivariate techniques we determine the number of key chemical species involved along the reaction paths and derive spectral and concentration profiles for the reaction intermediates. From the quantitative analysis of the XAS spectra we obtain accurate structural information for all reaction intermediates and provide the first structural characterization in solution of complex [N4Py·FeIII(OH)]2+. The employed strategy is promising for the spectroscopic characterization of transient species formed in redox reactions.
- Tavani, Francesco,Capocasa, Giorgio,Martini, Andrea,Sessa, Francesco,Di Stefano, Stefano,Lanzalunga, Osvaldo,D'Angelo, Paola
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supporting information
p. 131 - 142
(2021/01/11)
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- Tetrameric Lanthanide-Substituted Silicotungstate {Ln8Si4W40} Nanoclusters: Synthesis, Structural Characterization, Electrochemistry, and Catalytic Application for Oxidation of Thioethers
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All the title nanoclusters 1–10 with the molecular formula [(Ln2SiW10O38)4(W3O8)(OH)4(H2O)2]26? [LnIII =Sm (1), Eu (2), Gd (3), Tb (4), Dy (5), Ho (6), Er (7), Tm (8), Yb (9), and Y (10)] have been synthesized and isolated as mixed sodium and potassium salts. These nanoclusters are characterized by various analytical techniques such as FT-IR, UV/Vis, Photoluminescence, Single crystal X-ray diffraction, Electrochemistry, ICP-AES and Thermogravimetric analysis, and Powder X-ray diffraction. The {Ln8Si4W40} complexes show high efficiency and selectivity for the oxidation of thioethers using H2O2 as green oxidant. It is worth mentioning that the catalyst can be recovered even after five cycles of reaction with only a slight loss in its activity.
- Khan, Imran,Das, Vivek,Teillout, Anne-Lucie,Mbomekallé, Isra?l-Martyr,de Oliveira, Pedro,Sahoo, Subash Chandra,Hussain, Firasat
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supporting information
p. 1071 - 1081
(2021/03/16)
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- Synthesis of an anthraquinone-containing polymeric photosensitizer and its application in aerobic photooxidation of thioethers
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Work on the synthesis of a polymeric photosensitizer and its application in the photooxidation of thioethers is reported herein. Firstly, the polymeric photosensitizer was designed and synthesized by the reaction of anthraquinone-2-carbonyl chloride (AQ-2-COCl) with poly(2-hydroxyethyl methacrylate) (PHEMA). Then, the visible light-induced photooxidation of thioethers under aerobic conditions was investigated. The results revealed that the reaction yielded sulfoxides highly chemoselectively in excellent yields with good substrate tolerance. Importantly, AQ-PHEMA could be easily recovered and reused more than 20 times without significant loss of the catalytic activity.
- Chen, Yang,Ding, Aishun,Hu, Jianhua
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p. 10661 - 10665
(2020/03/27)
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- Selective oxidation of (hetero)sulfides with molecular oxygen under clean conditions
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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
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supporting information
p. 433 - 438
(2020/02/13)
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- Oxidation of aromatic sulfides with molecular oxygen: Controllable synthesis of sulfoxides or sulfones
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The recent development of selective oxidation of aromatic sulfides with molecular oxygen was highlighted. The sulfoxides and sulfones could be obtained by simply switching the reaction media, i.e., bis(2-butoxyethyl)ether (BBE) or poly(ethylene glycol)dimethyl ether (PEGDME). The application of the high-boiling-point polyether as an initiator and green media can eliminate the need of large quantities of additives and volatile solvents. This strategy represents an economic and eco-friendly method that could find potential applications.
- Tang, Lili,Du, Kejie,Yu, Bing,He, Liangnian
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p. 2991 - 2992
(2020/03/24)
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- Emodinas a novel organic photocatalyst for selective oxidation of sulfides under mild conditions
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Herein, we have developed naturally-occurringEmodin, which is commercially available at low-cost, as a novel organic photocatalyst for the first time.Emodinwas successfully employed in the selective oxidation of sulfides promoted by visible-light, deliver
- Li, Min,Lou, Jiangli,Rao, Yijian,Yuan, Zhenbo,Zhang, Yan
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p. 19747 - 19750
(2020/06/04)
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- The Hofmann reaction involving annulation of: O -(pyridin-2-yl)aryl amides selectively and rapidly leads to potential photocatalytically active 6 H -pyrido[1,2- c] quinazolin-6-one derivatives
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A highly efficient PIFA-mediated Hofmann reaction of o-(pyridin-2-yl)aryl amides has been developed to selectively and rapidly construct various potential photocatalytically active 6H-pyrido[1,2-c]quinazolin-6-one derivatives. The use of a nontoxic and ec
- Gao, Wenjing,Liu, Tongxin,Wan, Yameng,Wu, Hao,Zhang, Guisheng,Zhang, Zhiguo
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supporting information
p. 7955 - 7961
(2020/11/30)
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- B2cat2-Mediated Reduction of Sulfoxides to Sulfides
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An efficient and operationally simple method for the reduction of sulfoxides to sulfides has been developed using bis(catecholato)diboron (B2cat2) as a reducing agent. The present method accommodates various functional groups which are generally prone to reduction: halides, alkynes, carbonyls, nitriles, and heterocycles are totally intact, and only sulfoxide moieties undergo reduction chemoselectively. Moreover, the remaining diboron and the resulting boron-containing wastes are readily removable, the practicality of this protocol being thus demonstrated.
- Takahashi, Fumiya,Nogi, Keisuke,Yorimitsu, Hideki
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supporting information
p. 3009 - 3012
(2020/03/25)
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- A manganese(iii) Schiff base complex immobilized on silica-coated magnetic nanoparticles showing enhanced electrochemical catalytic performance toward sulfide and alkene oxidation
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In this study, a novel Mn(iii)-Schiff base complex was synthesized and characterized. The structure of this complex was determined to be a deformed octahedral coordination sphere by single-crystal X-ray diffraction analysis. The Mn(iii)-Schiff base complex was supported on silica-coated iron magnetic nanoparticlesviaaxial coordination by one-step complex anchoring to produce a heterogenized nanocatalyst. After this, the complex was characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), thermogravimetric analysis (TGA), vibrating sample magnetometry (VSM), and powder X-ray diffraction (XRD). Moreover, atomic absorption spectroscopy was used to determine the amount of the loaded metal. The heterogenized nanocatalyst effectively catalyzed the oxidation of a broad range of sulfides and alkenes with H2O2in the presence of a glassy carbon electrode, applying voltage to the reaction mixture. The results showed that the application of a potential to the reaction mixture could significantly decrease the reaction time when compared with the case of similar chemical oxidation reactions. In addition, an excellent value of turnover frequency (17?750 h-1) was achieved for the electrochemical oxidation of styrene. Moreover, the nanocatalyst showed good recoverability without significant loss of its activity within six successive runs in the electrochemical oxidation of methyl phenyl sulfide and cyclooctene. The electrochemical properties and stability of Fe3O4?SiO2-[MnL(OAc)] were investigated by cyclic voltammetry measurements and chronoamperometry technique.
- Elmi, Bahareh,Jafarian, Majid,Khodaei, Elham,Nafarieh, Parinaz,Rayati, Saeed,Wojtczak, Andrzej
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p. 17026 - 17036
(2020/05/18)
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- Unprecedented Reactivities of Highly Reactive Manganese(III)-Iodosylarene Porphyrins in Oxidation Reactions
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We report that Mn(III)-iodosylarene porphyrins, [MnIII(Porp)(sArIO)]+, are capable of activating the C-H bonds of hydrocarbons, including unactivated alkanes such as cyclohexane, with unprecedented reactivities, such as a low kinetic isotope effect, a saturation behavior of reaction rates, and no electronic effect of porphyrin ligands on the reactivities of [MnIII(Porp)(sArIO)]+. In oxygen atom transfer (OAT) reactions, the sulfoxidation of para-X-substituted thioanisoles by [MnIII(Porp)(sArIO)]+ affords a very unusual behavior in the Hammett plot with the saturation behavior of reaction rates and no electronic effect of porphyrin ligands on reactivities. The reactivities and mechanisms of [MnIII(Porp)(sArIO)]+ are then compared with those of the corresponding MnIV(Porp)(O) complex. The present study reports the first example of highly reactive Mn(III)-iodosylarene porphyrins with unprecedented reactivities in C-H bond activation and OAT reactions.
- Zhang, Lina,Lee, Yong-Min,Guo, Mian,Fukuzumi, Shunichi,Nam, Wonwoo
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supporting information
p. 19879 - 19884
(2020/11/27)
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- Selectivity switch in the aerobic oxygenation of sulfides photocatalysed by visible-light-responsive decavanadate
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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
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supporting information
p. 3896 - 3905
(2020/07/09)
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- Kinetic and mechanistic aspects of solid state, nanostructured porphyrin diacid photosensitizers in photooxidation of sulfides
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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
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p. 1260 - 1272
(2019/04/17)
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- Polymer-supported eosin Y as a reusable photocatalyst for visible light mediated organic transformations
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A novel polymer-supported recyclable photocatalyst has been developed for visible light mediated oxidation reactions. The organic dye eosin Y was loaded on macroporous commercially available Amberlite IRA 900 chloride resin and exploited as a photocatalyst for visible light mediated oxidation of thioethers to sulfoxides and phenylboronic acids to phenols under open atmospheric air. Varieties of functional groups were well tolerated during oxidation. The catalyst is recyclable for six cycles without significant loss in its efficiency. Furthermore, gram-scale oxidation of sulfides to sulfoxides has been demonstrated to prove the commercial viability of the method.
- Sridhar, Arunasalam,Rangasamy, Rajmohan,Selvaraj, Mari
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p. 17974 - 17979
(2019/12/02)
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- Imine-Based Covalent Organic Frameworks as Photocatalysts for Metal Free Oxidation Processes under Visible Light Conditions
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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
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p. 4916 - 4922
(2019/09/10)
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- Coupled X-ray Absorption/UV-vis Monitoring of Fast Oxidation Reactions Involving a Nonheme Iron-Oxo Complex
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Time-resolved X-ray absorption (XAS) and UV-vis spectroscopies with millisecond resolution are used simultaneously to investigate oxidation reactions of organic substrates by nonheme iron activated species. In particular, the oxidation processes of arylsulfides and benzyl alcohols by a nonheme iron-oxo complex have been studied. We show for the first time that the pseudo-first-order rate constants of fast bimolecular processes in solution (milliseconds and above) can be determined by time-resolved XAS technique. By following the Fe K-edge energy shift, it is possible to detect the rate of iron oxidation state evolution that matches that of the bimolecular reaction in solution. The kinetic constant values obtained by XAS are in perfect agreement with those obtained by means of the concomitant UV-vis detection. This combined approach has the potential to provide unique insights into reaction mechanisms in the liquid phase that involve changes of the oxidation state of a metal center, and it is particularly useful in complex chemical systems where possible interferences from species present in solution could make it impossible to use other detection techniques.
- Capocasa, Giorgio,Sessa, Francesco,Tavani, Francesco,Monte, Manuel,Olivo, Giorgio,Pascarelli, Sakura,Lanzalunga, Osvaldo,Di Stefano, Stefano,D'Angelo, Paola
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supporting information
p. 2299 - 2304
(2019/03/02)
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- Catalytic activity of Mn(III) porphyrins supported onto graphene oxide nano-sheets for green oxidation of sulfides
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In this research, oxidation of various sulfides with urea hydrogen peroxide (UHP) in the presence of manganese porphyrin grafted onto graphene oxide ([Mn(THPP)OAc@GO]) in ethanol was studied. The heterogenized catalyst was characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier-transform infrared (FT-IR), and UV–Vis spectroscopy. The amount of Mn-porphyrin loaded on the GO nano-sheets was determined by atomic absorption spectroscopy (AAS) and the thermal stability of the heterogenized catalyst was investigated by thermo-gravimetric analysis (TGA). [Mn(THPP)OAc@GO] was applied for the green oxidation of different sulfides and the solid catalyst can be simply reused several times without losing its catalytic efficiency.
- Rayati, Saeed,Rezaie, Saghar,Nejabat, Fatemeh
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p. 1466 - 1479
(2019/05/29)
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- Enzymatic kinetic resolution of chiral sulfoxides-an enantiocomplementary approach
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A new enzymatic assay for the preparation of chiral sulfoxides that is enantiocomplementary to the known (S)-enantiomer-reducing activity of methionine sulfoxide reductase A (MsrA) is described. To this end, we have utilized the enzyme DMSO reductase (DmsABC), recently discovered by us being highly upregulated in stationary phase E. coli bacteria.
- Nosek, Vladimír,Mí?ek, Ji?í
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supporting information
p. 10480 - 10483
(2019/09/07)
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- Aluminum(III) Chloride Promoted Oxygen Transfer: Selective Oxidation of Sulfides to Sulfoxides
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An efficient selective oxidation of sulfides to sulfoxides has been developed by means of AlCl 3 -promoted oxygen transfer from phenyliodine diacetate [PhI(OAc) 2 ]. AlCl 3 proved to be the optimalLewis acid for the activation of PhI(OAc) 2. Various substituted sulfides were selectively transformed into the corresponding sulfoxides in good to excellent yields (≤99%). The high efficiency, excellent functional-group compatibility, broad substrate scope, and mild conditions render the current transformation useful for the synthesis of sulfoxides.
- Xie, Yongtao,Li, Yuxin,Zhou, Sha,Zhou, Shaa,Zhang, Yan,Chen, Minggui,Li, Zhengming
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supporting information
p. 340 - 343
(2017/12/06)
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- Synthesis of: N -alkylated 2-pyridones through Pummerer type reactions of activated sulfoxides and 2-fluoropyridine derivatives
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N-Alkylated 2-pyridone products were obtained in good to excellent yields through a one-pot procedure involving either normal or interrupted Pummerer reactions between triflic anhydride activated sulfoxides and 2-fluoropyridine derivatives, followed by hydrolysis. This is a rare case that uses 2-fluoropyridine as a nucleophile in Pummerer type reactions.
- Hu, Gang,Xu, Jiaxi,Li, Pingfan
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p. 4151 - 4158
(2018/06/12)
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- A highly efficient reusable homogeneous copper catalyst for the selective aerobic oxygenation sulfides to sulfoxides
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Readily available copper showed efficient activity and great selectivity for the homogeneous catalysis of oxidation of sulfides to sulfoxides using molecular oxygen as the oxidant. The reaction proceeds under mild conditions in the presence of a catalytic amount of TEMPO. Importantly, the catalysts could be conveniently recovered and reused. And this methodology was proved to be applicable for the transformation of various aromatic and aliphatic sulfides into the corresponding sulfoxides with high conversion and high selectivity.
- Ren, Cheng,Fang, Runxing,Yu, Xiaochun,Wang, Shun
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supporting information
p. 982 - 986
(2018/02/13)
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- Chemoenzymatic Deracemization of Chiral Sulfoxides
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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
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supporting information
p. 9849 - 9852
(2018/07/31)
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- Synthesis method of aryl sulfoxide compound
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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 0067; 0068; 0069; 0070-0072; 0111; 0116; 0121
(2017/07/20)
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- Mn-Schiff base complex supported on magnetic nanoparticles: Synthesis, crystal structure, electrochemical properties and catalytic activities for oxidation of olefins and sulfides
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A novel, magnetically recoverable Mn-Schiff base catalyst has been prepared by the adsorption on silica-coated magnetic nanoparticles. X-ray crystallography studies reveal that the Mn-complex adopt a distorted octahedral six-coordinate configuration formed by the tetradentate Schiff base ligand and two oxygen atoms of acetate anion. The heterogeneous catalyst was characterized by powder X-ray diffraction, transmission electron microscopy, scanning electron microscopy, vibrating sample magnetometer, thermo-gravimetric analysis, the energy-dispersive X-ray spectroscopy and FTIR spectroscopy. The catalyst loading on the magnetic support was determined by atomic absorption spectroscopy. Highly chemoselective oxidation of sulfides with excellent yield to the corresponding sulfoxides, and epoxidation of olefins in ethanol at room temperature were efficiently enhanced under the influence of the magnetically separable catalyst. The separation and recycling of the catalyst is simple, effective, and economic in this clean oxidation method. The electrochemical properties of the Mn-complex were investigated.
- Rayati, Saeed,Khodaei, Elham,Jafarian, Majid,Wojtczak, Andrzej
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p. 327 - 335
(2017/06/21)
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- Immobilized molybdenum acetylacetonate complex on expanded starch for chemoselective oxidation of sulfides to sulfoxides with t-BuOOH at room temperature
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We explored a highly efficient protocol for the oxidation of alkyl aryl sulfides to sulfoxides with high selectivities catalyzed by a molybdenum acetylacetonate complex immobilized on expanded corn starch (ECS-MoO2(acac)2) in the pre
- Hong, Mei,Yan, Jun-Min
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p. 985 - 988
(2017/09/08)
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- Catalytic activity and electrochemical properties of Cu(II)-Schiff base complex encapsulated in the nanocavities of zeolite-Y for oxidation of olefins and sulfides
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Copper(II) complex of a Schiff base ligand (H2L) was synthesized, characterized, and encapsulated in the cavities of zeolite-Y by a fixed ligand method. The zeolite encapsulated metal complex (CuL-Y) was characterized using FT-IR, UV–Vis and atomic absorption spectroscopy, thermogravimetric analysis (TGA), X-ray powder diffraction (XRD), scanning electron microscopy images (SEM), energy-dispersive X-ray spectroscopy (EDX), and Brunauer-Emmett-Teller (BET). The catalytic activity and electrochemical behavior of the encapsulated complex has been studied in the oxidation of a wide range of sulfides and olefins using H2O2 in ethanol. This heterogeneous catalytic system shows a dramatic increase in total turnover number (46,500) for oxidation of styrene. It could be readily reused for at least eight successive times without discernible activity and selectivity deterioration, which displays potential for practical applications.
- Rayati, Saeed,Khodaei, Elham,Jafarian, Majid
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p. 2736 - 2750
(2017/09/06)
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- Peroxygenase-Catalyzed Enantioselective Sulfoxidations
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The performances of the unspecific peroxigenase from Agrocybe aegerita (AaeUPO) in the asymmetric sulfoxidation of substituted aryl alkyl sulfides were here investigated. A small library of differently substituted aryl alkyl sulfoxides was successfully synthesized from the corresponding sulfides in the presence of AaeUPO and H2O2. All the sulfoxides were obtained as (R)-enantiomers, regardless the substitution pattern both on the aromatic ring and the alkyl chain, in up to > 99 % conversion and > 99 % ee. An overview about the biocatalytic entries to chiral sulfoxides is also presented here in form of a comparison between the results obtained with AaeUPO and performances of the chloroperoxidase from Caldariomyces fumago, and three different Baeyer–Villiger monooxygenases. To the best our knowledge, this is the first example of a systematic investigation of the AaeUPO synthetic potential in the asymmetric oxidation of hetero atoms, i.e., the pro-stereogenic sulfur of sulfides.
- Bassanini, Ivan,Ferrandi, Erica Elisa,Vanoni, Marta,Ottolina, Gianluca,Riva, Sergio,Crotti, Michele,Brenna, Elisabetta,Monti, Daniela
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supporting information
p. 7186 - 7189
(2017/12/28)
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- Sulfoxidation inside a C3-vanadium(V) bowl-shaped catalyst
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The confined enantiopure oxido-vanadium complex SSS-RRR-1 was synthesized and tested as a catalyst for the oxidation of sulfides into sulfoxides. This catalyst is very efficient with a reaction rate more than 300 times higher than that of the model compound SSS-RRR-3, and a turnover number (TON) close to 105 was reached in combination with a good selectivity (more than 90%) in the sulfoxide product. Moreover, enantiomerically enriched sulfoxide can be obtained, breaking through the major limitation of the previous chiral vanatrane catalysts that show no detectable enantiomeric excess (ee). Further investigations revealed that the complex SSS-RRR-1 adopts a bowl-shaped structure with an open hydrophobic pocket. The microenvironment of the chiral pocket above the metal center accounts for the strong improvement in catalytic activity and enantioselectivity.
- Zhang, Dawei,Dutasta, Jean-Pierre,Dufaud, Veronique,Guy, Laure,Martinez, Alexandre
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p. 7340 - 7345
(2017/11/09)
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- Direct Irradiaton of Aryl Sulfides: Homolytic Fragmentation and Sensitized S-Oxidation
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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
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p. 9054 - 9065
(2017/09/11)
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- Oxidation of sulfides using recyclable pseudocyclic benziodoxole triflate
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A new pseudocyclic hypervalent iodine reagent, benziodoxole triflate (IBA-OTf, a complex of 2-iodosylbenzoic acid with trifluoromethanesulfonic acid), can be used as an efficient oxidant for selective oxidation of various organic sulfides to sulfoxides. This oxidation proceeds under mild condition to afford the corresponding sulfoxides in moderate to good yields without overoxidation. The reduced form of the hypervalent iodine reagent, 2-iodobenzoic acid, can be easily recovered from the reaction mixture in good yields by a simple acid-base liquid-liquid biphasic protocol. (Chemical Equation Presented).
- Yoshimura, Akira,Zhdankin, Viktor V.
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- Pt(II) coordination complexes as visible light photocatalysts for the oxidation of sulfides using batch and flow processes
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A new catalytic system for the photooxidation of sulfides based on Pt(ii) complexes is presented. The catalyst is capable of oxidizing a large number of sulfides containing aryl, alkyl, allyl, benzyl, as well as more complex structures such as heterocycles and methionine amino acid, with complete chemoselectivity. In addition, the first sulfur oxidation in a continuous flow process has been developed.
- Casado-Sánchez, Antonio,Gómez-Ballesteros, Rocío,Tato, Francisco,Soriano, Francisco J.,Pascual-Coca, Gustavo,Cabrera, Silvia,Alemán, José
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supporting information
p. 9137 - 9140
(2016/07/21)
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- Supramolecular Activation of Hydrogen Peroxide in the Selective Sulfoxidation of Thioethers by a Self-Assembled Hexameric Capsule
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An efficient metal-free organocatalytic activation of hydrogen peroxide (H2O2) towards thioethers leading to the corresponding sulfoxides in high yields at room temperature within hours was promoted by the hexameric capsule formed by
- La Sorella, Giorgio,Sperni, Laura,Strukul, Giorgio,Scarso, Alessandro
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p. 3443 - 3449
(2016/11/13)
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- Visible light catalyzed methylsulfoxidation of (het)aryl diazonium salts using DMSO
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The visible light catalyzed methylsulfoxidation of (het)aryl diazonium salts using DMSO is illustrated. This is the first example of DMSO being used as the source of the methylsulfinyl group. The procedure tolerates a wide range of functional groups on (het)aryl diazonium salts and provides aryl methyl sulfoxides in excellent yields under mild reaction conditions.
- Pramanik, Mukund M. D.,Rastogi, Namrata
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supporting information
p. 8557 - 8560
(2016/07/13)
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- Manganese- and Lanthanide-Based 1D Chiral Coordination Polymers as an Enantioselective Catalyst for Sulfoxidation
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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.
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supporting information
p. 2701 - 2708
(2016/04/05)
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- Efficient Epoxidation of Styrene Derivatives by a Nonheme Iron(IV)-Oxo Complex via Proton-Coupled Electron Transfer with Triflic Acid
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Styrene derivatives are not oxidized by [(N4Py)FeIV(O)]2+ (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) in acetonitrile at 298 K, whereas epoxidation of styrene derivatives by the iron(IV)-oxo complex occurs efficiently in the presence of triflic acid (HOTf) via proton-coupled electron transfer (PCET) from styrene derivatives to the diprotonated species of [(N4Py)FeIV(O)]2+ with HOTf. Logarithms of the first-order rate constants of HOTf-promoted expoxidation of styrene derivatives with [(N4Py)FeIV(O)]2+ and PCET from electron donors to [(N4Py)FeIV(O)]2+ in the precursor complexes exhibit a remarkably unified correlation with the driving force of PCET in light of the Marcus theory of electron transfer when the differences in the formation constants of precursor complexes are taken into account. The same PCET driving force dependence is obtained for the first-order rate constants of HOTf-promoted oxygen atom transfer from thioanisols to [(N4Py)FeIV(O)]2+ and HOTf-promoted hydrogen atom transfer from toluene derivatives to [(N4Py)FeIV(O)]2+ in the precursor complexes. Thus, HOTf-promoted epoxidation of styrene derivatives by [(N4Py)FeIV(O)]2+ proceeds via the rate-determining electron transfer from styrene derivatives to the diprotonated species of [(N4Py)FeIV(O)]2+, as shown in the reactions of HOTf-promoted oxygen atom transfer from thioanisols to [(N4Py)FeIV(O)]2+ and HOTf-promoted hydrogen atom transfer from toluene derivatives to [(N4Py)FeIV(O)]2+.
- Park, Jiyun,Lee, Yong-Min,Ohkubo, Kei,Nam, Wonwoo,Fukuzumi, Shunichi
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supporting information
p. 5806 - 5812
(2015/06/25)
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- Kinetic and mechanistic studies of the reactivity of iron(IV) TAMLs toward organic sulfides in water: Resolving a fast catalysis versus slower single-turnover reactivity dilemma
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TAML complex [FeIII{C6H4-1,2-(NCOCMe2NCO)2CMe2}OH2]- (1) is oxidized by H2O2 or tBuOOH in water at pH 2O2 catalyzed by 1 has been studied under steady-state conditions. Covering the concentration of 1 in a 100-fold range has revealed that though first-order kinetics in 1 is observed at low catalyst concentrations (below 10-6 M), there is a significant negative deviation from linearity at [1] > 10-6 M. The latter was rationalized by the equilibrium between the monomeric and dimeric FeIV species 2 M M-M (Kd), both being able to oxidize p-NO2C6H4SMe with rate constants km and kd which were found to be (13 ± 1) × 104 and (0.32 ± 0.01) × 104 M-1 s-1, respectively. The difference in the rate constants is the key for resolving the dilemma of faster catalysis versus slower single-turnover reactivity of TAML activators in water.
- Banerjee, Deboshri,Ryabov, Alexander D.,Collins, Terrence J.
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p. 3032 - 3045
(2015/09/22)
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- Synthesis and oxidation catalysis of a Ti-substituted phosphotungstate, and identification of the active oxygen species
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In this paper, we report the synthesis of a Ti-substituted phosphotungstate, TBA6[(γ-PW10O36)2Ti4(μ-O)2(μ-OH)4] (I, TBA = tetra-n-butylammonium), and its application to H2O2-based oxidation. Firstly, an organic solvent-soluble dilacunary phosphotungstate precursor, TBA3[γ-PW10O34(H2O)2] (PW10), has been synthesized. By the reaction of PW10 and TiO(acac)2 (acac = acetylacetonate) in an organic medium (acetonitrile), I can be obtained. Compound I possesses a tetranuclear Ti core which can effectively activate H2O2 and shows high catalytic performance for several oxidation reactions, such as epoxidation of alkenes, oxygenation of sulfides, oxidative bromination of unsaturated compounds, and hydroxylation of anisole, giving the corresponding oxidation products with high efficiencies and selectivities. The catalytic performance of I is much superior to those of previously reported Ti-substituted polyoxometalates. In addition, I is highly durable during catalysis and can be reused several times while keeping its high catalytic performance. Furthermore, we have successfully isolated the truly catalytically active species for the present I-catalyzed oxidation, TBA6[(γ-PW10O36)2Ti4(μ-η2:η2-O2)4] (II), and its anion structure has been determined by X-ray crystallographic analysis. All of the four Ti2-μ-η2:η2-peroxo species in II are active for stoichiometric oxidation (without H2O2), and II is included in the catalytic cycle for I-catalyzed oxidation.
- Takahashi, Eri,Kamata, Keigo,Kikukawa, Yuji,Sato, Sota,Suzuki, Kosuke,Yamaguchi, Kazuya,Mizuno, Noritaka
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p. 4778 - 4789
(2015/10/05)
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- Synthesis, structural, spectral, electrochemical and catalytic properties of VO (IV) complexes containing N, O donors
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Complexes of the general formula M (X-DPMP)2[where, (M = VOIV), DPMP = 2-[(2,6-Diisopropyl-phenylimino)-methyl]-phenol and X = Br, BrCl, Ph] have been synthesized and characterized by IR, electronic, ESR spectral, magnetic and cyclic voltammetry measurements. The newly synthesized Schiff bases act as monobasic bidentate ligand in their complexes. The spectral data indicate that the ligand coordinates through the phenolic oxygen and azomethine nitrogen atoms. The observed parameters, hyperfine splitting constant (A) and Landé splitting energy (g) are found to be in good agreement with the values generally observed for the vanadyl complex with square pyramidal geometry. The cyclic voltammetric redox potentials of VO (IV) complexes suggest the existence of irreversible pairs in acetonitrile. The vanadium complexes were screened for sulfide oxidation studies and VO (C19H21BrON)2or [VO (Br-DPMP)2] was found to be an efficient catalyst for the oxidation of various sulfides to sulfoxides with PhIO terminal oxidant. Both aryl and alkyl sulfides were selected and converted into sulfoxides in good to excellent yields.
- Kanmani Raja,Lekha,Hariharan,Easwaramoorthy,Rajagopal
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p. 227 - 233
(2014/12/10)
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- Metal-free chemoselective oxidation of sulfides by in situ generated Koser's reagent in aqueous media
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Selective oxidation of sulfides was successfully performed by employing phenyliodine diacetate as an oxidant with the catalysis of TsOH in aqueous solution under mild conditions. Sulfoxides were formed with 1.1 equiv of PhI(OAc)2 at room temperature; whereas sulfones were obtained in the presence of 2.1 equiv of PhI(OAc)2 at 80 C under otherwise identical conditions. Notably, various sulfides were converted to corresponding sulfoxides or sulfones in good to high yields by this metal-free protocol.
- Yu, Bing,Guo, Chun-Xiang,Zhong, Chun-Lai,Diao, Zhen-Feng,He, Liang-Nian
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supporting information
p. 1818 - 1821
(2014/03/21)
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- Unified view of oxidative C-H bond cleavage and sulfoxidation by a nonheme iron(IV)-oxo complex via lewis acid-promoted electron transfer
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Oxidative C-H bond cleavage of toluene derivatives and sulfoxidation of thioanisole derivatives by a nonheme iron(IV)-oxo complex, [(N4Py)Fe IV(O)]2+ (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl) methylamine), were remarkably enhanced by the presence of triflic acid (HOTf) and Sc(OTf)3 in acetonitrile at 298 K. All the logarithms of the observed second-order rate constants of both the oxidative C-H bond cleavage and sulfoxidation reactions exhibit remarkably unified correlations with the driving forces of proton-coupled electron transfer (PCET) and metal ion-coupled electron transfer (MCET) in light of the Marcus theory of electron transfer when the differences in the formation constants of precursor complexes between PCET and MCET were taken into account, respectively. Thus, the mechanisms of both the oxidative C-H bond cleavage of toluene derivatives and sulfoxidation of thioanisole derivatives by [(N4Py)FeIV(O)]2+ in the presence of HOTf and Sc(OTf)3 have been unified as the rate-determining electron transfer, which is coupled with binding of [(N4Py)FeIV(O)]2+ by proton (PCET) and Sc(OTf)3 (MCET). There was no deuterium kinetic isotope effect (KIE) on the oxidative C-H bond cleavage of toluene via the PCET pathway, whereas a large KIE value was observed with Sc(OTf)3, which exhibited no acceleration of the oxidative C-H bond cleavage of toluene. When HOTf was replaced by DOTf, an inverse KIE (0.4) was observed for PCET from both toluene and [Ru II(bpy)3]2+ (bpy =2,2′-bipyridine) to [(N4Py)FeIV(O)]2+. The PCET and MCET reactivities of [(N4Py)FeIV(O)]2+ with Bronsted acids and various metal triflates have also been unified as a single correlation with a quantitative measure of the Lewis acidity.
- Park, Jiyun,Morimoto, Yuma,Lee, Yong-Min,Nam, Wonwoo,Fukuzumi, Shunichi
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supporting information
p. 3618 - 3628
(2014/05/06)
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