- On the mechanism of the oxygen transfer to sulfoxides by (peroxo)[tris(hydroxyalkyl)amine]TiIV complexes - Evidence for a metal-template-assisted process
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Oxidation of p-XC6H4SOMe (X = NC, F3C) by (alkylperoxo)-(tris[(2R)-2-hydroxy-2-phenylethyl]amine}titanium (2b) has been shown to follow Michaelis-Menten kinetics demonstrating the occurrence of an intramolecular nucleophilic oxygen transfer to the TiIV-coordinated sulfoxide. The reaction of the titanium(IV) precursors 1 with sulfoxides has been studied by ESI-MS techniques together with ab initio calculations. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
- Bonchio, Marcella,Bortolini, Olga,Licini, Giulia,Moro, Stefano,Nugent, William A.
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Read Online
- 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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- High Chemoselectivity in the Construction of Aryl Methyl Sulfones via an Unexpected C-S Bond Formation between Sulfonylhydrazides and Dimethyl Phosphite
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A highly chemoselective route to aryl methyl sulfones via an unexpected C S bond formation between sulfonylhydrazides and dimethyl phosphite catalyzed by NaI under mild conditions has been established. This transformation provides an alternative and metal-free pathway to acquire various aryl methyl sulfones in good to excellent yields. Notably, dimethyl phosphite was employed as a stable and readily available alkyl source.
- Liu, Teng,Yu, Shiwen,Shen, Xiang,Li, Yixian,Liu, Jianjun,Huang, Chao,Cheng, Feixiang
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p. 153 - 160
(2021/10/04)
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- Nickel-Catalyzed Cyanation of Aryl Thioethers
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A nickel-catalyzed cyanation of aryl thioethers using Zn(CN)2 as a cyanide source has been developed to access functionalized aryl nitriles. The ligand dcype (1,2-bis(dicyclohexylphosphino)ethane) in combination with the base KOAc (potassium acetate) is essential for achieving this transformation efficiently. This reaction involves both a C-S bond activation and a C-C bond formation. The scalability, low catalyst and reagents loadings, and high functional group tolerance have enabled both late-stage derivatization and polymer recycling, demonstrating the reaction's utility across organic chemistry.
- Delcaillau, Tristan,Woenckhaus-Alvarez, Adrian,Morandi, Bill
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supporting information
p. 7018 - 7022
(2021/09/13)
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- Decarbonylative Synthesis of Aryl Nitriles from Aromatic Esters and Organocyanides by a Nickel Catalyst
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A decarbonylative cyanation of aromatic esters with aminoacetonitriles in the presence of a nickel catalyst was developed. The key to this reaction was the use of a thiophene-based diphosphine ligand, dcypt, permitting the synthesis of aryl nitrile without the generation of stoichiometric metal- or halogen-containing chemical wastes. A wide range of aromatic esters, including hetarenes and pharmaceutical molecules, can be converted into aryl nitriles.
- Iizumi, Keiichiro,Kurosawa, Miki B.,Isshiki, Ryota,Muto, Kei,Yamaguchi, Junichiro
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supporting information
p. 1555 - 1559
(2020/11/10)
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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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- Ceramic boron carbonitrides for unlocking organic halides with visible light
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Photochemistry provides a sustainable pathway for organic transformations by inducing radical intermediates from substrates through electron transfer process. However, progress is limited by heterogeneous photocatalysts that are required to be efficient, stable, and inexpensive for long-term operation with easy recyclability and product separation. Here, we report that boron carbonitride (BCN) ceramics are such a system and can reduce organic halides, including (het)aryl and alkyl halides, with visible light irradiation. Cross-coupling of halides to afford new C-H, C-C, and C-S bonds can proceed at ambient reaction conditions. Hydrogen, (het)aryl, and sulfonyl groups were introduced into the arenes and heteroarenes at the designed positions by means of mesolytic C-X (carbon-halogen) bond cleavage in the absence of any metal-based catalysts or ligands. BCN can be used not only for half reactions, like reduction reactions with a sacrificial agent, but also redox reactions through oxidative and reductive interfacial electron transfer. The BCN photocatalyst shows tolerance to different substituents and conserved activity after five recycles. The apparent metal-free system opens new opportunities for a wide range of organic catalysts using light energy and sustainable materials, which are metal-free, inexpensive and stable. This journal is
- Yuan, Tao,Zheng, Meifang,Antonietti, Markus,Wang, Xinchen
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p. 6323 - 6332
(2021/05/19)
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- COMPOSITES, METHODS AND USES THEREOF
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The present invention relates, in general terms, to methods of catalysing a reaction, including the steps of contacting a chemical entity comprising a sulphide moiety with a composite and an oxidant. The composite acts as a heterogeneous catalyst to oxidise the sulphide moiety. The present invention also relates to composites, methods of synthesising the composites and its use as a catalyst thereof.
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Page/Page column 26
(2021/06/04)
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- Nickel-Catalyzed Reversible Functional Group Metathesis between Aryl Nitriles and Aryl Thioethers
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We describe a new functional group metathesis between aryl nitriles and aryl thioethers. The catalytic system nickel/dcype is essential to achieve this fully reversible transformation in good to excellent yields. Furthermore, the cyanide- and thiol-free reaction shows high functional group tolerance and great efficiency for the late-stage derivatization of commercial molecules. Finally, synthetic applications demonstrate its versatility and utility in multistep synthesis.
- Delcaillau, Tristan,Boehm, Philip,Morandi, Bill
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supporting information
p. 3723 - 3728
(2021/04/07)
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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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- 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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- Single-Molecule Magnetic, Catalytic and Photoluminescence Properties of Heterometallic 3d–4f [Ln{PZn2W10O38(H2O)2}2]11? Tungstophosphate Nanoclusters
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A series of eleven lanthanide containing di-Zinc (II) substituted heterometallic 3d–4f sandwich-type tungstophosphate nanoclusters [Ln{PZn2W10O38(H2O)2}2]11? (Ln=NdIII, SmIII, EuIII, GdIII, TbIII, DyIII, HoIII, ErIII, TmIII, YbIII, and LuIII) have been synthesized by a single step reaction procedure. These clusters were characterized by various analytical techniques such as single crystal X-ray diffraction (SC-XRD), fourier transform infrared (FT-IR) spectroscopy, high-resolution electro-spray ionization mass spectrometry (HR-ESI-MS), inductively coupled plasma atomic emission spectroscopy (ICP-AES), solid UV/Vis, photoluminescence spectroscopy, powder X-ray diffraction (P-XRD) and thermogravimetric analysis (TGA). All the polyanions are isostructural and consists of a lanthanide ion sandwiched between two units of (1,5) isomer of di-Zn substituted α-Keggin type tungstophosphate. The complexes Sm-2 a, Eu-3 a, Tb-5 a, and Dy-6 a show good photoluminescence behavior. The catalytic properties were examined for the oxidation of thioethers. The catalyst is stable with a high turn over frequency (TOF) of 6250 h?1 and can be recovered even after 5 consecutive cycles. Furthermore, magnetic properties revealed that Gd-4 a, Tb-5 a, Dy-6 a, Er-8 a, and Yb-10 a show single-molecule magnetic properties.
- Das, Vivek,Khan, Imran,Hussain, Firasat,Sadakane, Masahiro,Tsunoji, Nao,Ichihashi, Katsuya,Kato, Chisato,Inoue, Katsuya,Nishihara, Sadafumi
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p. 3819 - 3831
(2021/09/22)
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- General sulfone construction: Via sulfur dioxide surrogate control
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A highly efficient one-step synthesis of alkyl-alkyl and aryl-alkyl sulfones with a facile combination of halides, sulfur dioxide surrogates and phosphate esters is described. When thiourea dioxide was employed as a reductive sulfur dioxide surrogate, alkyl-alkyl sulfones were obtained under transition metal free conditions. Aryl-alkyl sulfones were obtained with an extremely low catalytic loading (0.2 mol%) via altering the mask of sulfur dioxide surrogates to sodium dithionite. A phosphate ester was employed as a stable and readily available alkyl source. Notably, this protocol has been applied to the late-stage modification of natural products and bioactive molecules.
- Chen, Shihao,Li, Yaping,Wang, Ming,Jiang, Xuefeng
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supporting information
p. 322 - 326
(2020/02/13)
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- Nickel-Catalyzed Cyanation of Aryl Halides and Hydrocyanation of Alkynes via C-CN Bond Cleavage and Cyano Transfer
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We report nickel-catalyzed cyanation and hydrocyanation methods to prepare aryl nitriles and vinyl nitriles from aryl halides and alkynes, respectively. Using inexpensive and nontoxic 4-cyanopyridine N-oxide as the cyano shuttle, the methods provide an efficient approach to prepare aryl cyanides and vinyl nitriles under mild and operationally simple reaction conditions with a broad range of functional group tolerances. In hydrocyanation of alkynes, the method demonstrated good regioselectivity, producing predominantly E- or Z-alkenyl nitriles in a controlled manner and exclusively Markovnikov vinyl nitriles when internal diaryl alkynes and terminal alkynes were applied as the substrates, respectively. The preliminary mechanistic investigation indicated that the C-CN bond cleavage process is promoted by oxidative addition to the nickel(I) complex in the cyanation of aryl halides, and further studies via a series of deuterium exchange experiments indicated that water serves as the hydrogen source for the hydrocyanation of alkynes.
- Chen, Hui,Sun, Shuhao,Liu, Yahu A.,Liao, Xuebin
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p. 1397 - 1405
(2020/02/04)
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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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- 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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- 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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- Synthesis of Na22[((RE)4(H2O)6Sb6O4)(SbW10O37)2(SbW8O31)2] [(RE)III = Y, Gd, Tb, Dy, Ho, Er, Tm, Yb]: Synthesis, characterization and catalytic application
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A series of eight rare-earth substituted antimony tungstates with the formulae [((RE)4(H2O)6Sb6O4)(SbW10O37)2(SbW8O31)2]22– [(RE)III = Y(1), Gd(2), Tb(3), Dy(4), Ho(5), Er(6), Tm(7), Yb(8)] has been synthesized under ambient conditions. The compounds were isolated using rare-earth salts and Na9[B-α-SbW9O33]?19.5 H2O as precursors along with sodium dihydrogen phosphate in 1 M NaCl solution. The addition of dihydrogen phosphate was found to be a crucial step for the isolation of these polyanions. The polyanions were characterized by various analytical techniques such as single crystal X-ray diffraction (1a – 6a) (SC-XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA). The compounds were found to show efficient heterogeneous catalytic activity for oxidation of thioethers.
- Gupta, Rakesh,Hussain, Firasat,Kaushik, Reetam,Khan, Imran
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- A convenient reagent for the conversion of aldoximes into nitriles and isonitriles
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For the dehydroxylation of aldoximes with 4-nitro-1-((trifluoromethyl)sulfonyl)-imidazole (NTSI), slight modifications of reaction conditions resulted in significantly different reaction paths to provide either nitriles or isonitriles. The challenging conversion of aldoximes into isonitriles was achieved under mild conditions.
- Zhang, Wei,Lin, Jin-Hong,Zhang, Pengfei,Xiao, Ji-Chang
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supporting information
p. 6221 - 6224
(2020/06/29)
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- A Transition-Metal-Free One-Pot Cascade Process for Transformation of Primary Alcohols (RCH2OH) to Nitriles (RCN) Mediated by SO2F2
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A new transition-metal-free one-pot cascade process for the direct conversion of alcohols to nitriles was developed without introducing an “additional carbon atom”. This protocol allows transformations of readily available, inexpensive, and abundant alcohols to highly valuable nitriles.
- Jiang, Ying,Sun, Bing,Fang, Wan-Yin,Qin, Hua-Li
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p. 3190 - 3194
(2019/05/21)
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- Organic photoredox catalysis enabled cross-coupling of arenediazonium and sulfinate salts: Synthesis of (un)symmetrical diaryl/alkyl aryl sulfones
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We disclose herein the first transition-metal-and external oxidant/reductant-free visible-light-mediated synthesis of (un)symmetrical diaryl/alkyl aryl sulfones from arenediazonium tetrafluoroborates and sodium sulfinates using eosin Y as an organic photoredox catalyst. The utilization of visible light as an inexpensive and ecosustainable energy source, operational simplicity, ambient temperature and clean reaction in aqueous acetonitrile are the salient features of the developed protocol. The desired sulfones were also synthesized via a one-pot, two-step process directly from anilines and sulfinate salts in good to excellent yields.
- Chawla, Ruchi,Yadav, Lal Dhar S.
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supporting information
p. 4761 - 4766
(2019/05/24)
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- A Convenient Synthesis of Sulfones via Light Promoted Coupling of Sodium Sulfinates and Aryl Halides
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A convenient and e?cient synthesis of sulfones from sulfinates and aryl halides was developed. The reaction occurred under UV irradiation without transition metal catalyst or photocatalyst. A radical pathway via single-electron transfer (SET) of electron donor-acceptor (EDA) complex was proposed based on UV-vis spectroscopy, radical inhibiting and trapping experiments. (Figure presented.).
- Chen, Lei,Liang, Jie,Chen, Zhen-yu,Chen, Jie,Yan, Ming,Zhang, Xue-jing
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p. 956 - 960
(2019/01/25)
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- Cascade Process for Direct Transformation of Aldehydes (RCHO) to Nitriles (RCN) Using Inorganic Reagents NH2OH/Na2CO3/SO2F2 in DMSO
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A simple, mild, and practical process for direct conversion of aldehydes to nitriles was developed feathering a wide substrate scope and great functional group tolerability (52 examples, over 90% yield in most cases) using inorganic reagents (NH2OH/Na2CO3/SO2F2) in DMSO. This method allows for transformations of readily available, inexpensive, and abundant aldehydes to highly valuable nitriles in a pot, atom, and step-economical manner without transition metals. This protocol will serve as a robust tool for the installation of cyano-moieties to complicated molecules.
- Fang, Wan-Yin,Qin, Hua-Li
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p. 5803 - 5812
(2019/05/14)
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- SO 2 F 2 -Promoted Dehydration of Aldoximes: A Rapid and Simple Access to Nitriles
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A rapid, simple and mild process for the dehydration of aldoximes to give the corresponding nitriles, which utilizes SO 2 F 2 as an efficient reagent, has been developed. A variety of (hetero)arene, alkene, alkyne and aliphatic aldoximes proceeded with high efficiency to afford nitriles in excellent to quantitative yields with great functional group compatibilities in acetonitrile under ambient conditions. Furthermore, an eco-friendly synthetic protocol to access nitriles from aldehydes with ortho -, meta - and para -nitrile groups was also described in aqueous methanol by using inorganic base Na 2 CO 3, and a one-pot synthetic strategy to generate nitriles from aldehydes was proved to be feasible.
- Ding, Chengrong,Mei, Guangyao,Wang, Haibo,Zhang, Guofu,Zhao, Yiyong
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p. 1484 - 1488
(2019/07/15)
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- HETEROCYCLIC CARBOXYLIC ACID AMIDE LIGAND AND APPLICATIONS THEREOF IN COPPER CATALYZED COUPLING REACTION OF ARYL HALOGENO SUBSTITUTE
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Provided are a heterocyclic carboxylic acid amide ligand and applications thereof in a copper catalyzed coupling reaction. Specifically, provided are uses of a compound represented by formula (I), definitions of radical groups being described in the specifications. The compound represented by formula (I) can be used as the ligand in the copper catalyzed coupling reaction of the aryl halogeno substitute, and is used or catalyzing the coupling reaction for forming the aryl halogeno substitute having C—N, C—O, C—S and other bonds.
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Paragraph 0293-0294
(2019/05/15)
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- Electrochemical oxidations of thioethers: Modulation of oxidation potential using a hydrogen bonding network
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A highly efficient chemo-selective electrochemical oxidation of thioethers to sulfoxides and sulfones was developed. The hydrogen bonding network generated from hexafluoro-2-propanol (HFIP) and acetic acid (AcOH) plays an important role in the modulation of oxidation potential. The hydrogen bonding network complexes strongly with the sulfoxide, making it less prone to further oxidation. Therefore, thioethers can be selectively electrochemically oxidized to sulfoxides and over-oxidization could be minimized. Moreover, this modulation of oxidization via hydrogen bonding was supported by density functional theory (DFT) calculations and cyclic voltammetry experiments.
- Liu, Shiwen,Chen, Bocheng,Yang, Yi,Yang, Yuhao,Chen, Qianjin,Zeng, Xiaojun,Xu, Bo
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- Method for preparing aryl sulfone compound as well as method for extracting catalyst and aryl sulfone compound
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The invention provides a preparation method of an aryl sulfone compound, which is characterized in that in an organic solvent and under an aerobic atmosphere, a catalytic system composed of a metal-ligand-TEMPO is used for catalytic oxidation of a thioether compound to obtain the aryl sulfone compound. The preparation method is simple, green, and efficient, the reaction condition is mild, and theapplication range is wide; the invention also provides a method for extracting a catalyst and the product aryl sulfone compound used in the preparation process. The ethyl acetate is added to a reaction mixture, steps of filtering and condensation under reduced pressure are carried out to obtain a filtrate and the catalyst, and silica gel column chromatography and concentration extraction are carried out to obtain the aryl sulfone compound. The extraction method is simple, and the extracted catalyst has high activity and good cycle stability, and the extraction rate of the product aryl sulfonecompound is high.
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Paragraph 0096-0099
(2019/02/13)
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- A Class of Amide Ligands Enable Cu-Catalyzed Coupling of (Hetero)aryl Halides with Sulfinic Acid Salts under Mild Conditions
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The amide derived from 4-hydroxy-l-proline and 2,6-dimethylaniline is a powerful ligand for Cu-catalyzed coupling of (hetero)aryl halides with sulfinic acid salts, allowing the formation of a wide range of (hetero)aryl sulfones from the corresponding (hetero)aryl halides at considerably low catalytic loadings. The coupling of (hetero)aryl iodides and sodium methanesulfinate proceeds at room temperature with only 0.5 mol % CuI and ligand, representing the first example for Cu-catalyzed arylation at both low catalytic loading and room temperature.
- Zhao, Jinlong,Niu, Songtao,Jiang, Xi,Jiang, Yongwen,Zhang, Xiaojing,Sun, Tiemin,Ma, Dawei
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p. 6589 - 6599
(2018/05/31)
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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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- An Efficient Oxidation of Sulfides to Sulfones with Urea-Hydrogen Peroxide in the Presence of Phthalic Anhydride in Ethyl Acetate
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A metal-free, environmentally benign oxidation of substituted sulfides directly to their corresponding sulfones is described. Using urea-hydrogen peroxide and phthalic anhydride in ethyl acetate clean conversion into the sulfone was achieved without observation of the possible sulfoxide oxidation product.
- Lutz, Marlon,Wenzler, Marta,Likhotvorik, Igor
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supporting information
p. 2231 - 2234
(2018/04/16)
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- Copper-catalyzed: S -methylation of sulfonyl hydrazides with TBHP for the synthesis of methyl sulfones in water
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A copper-catalyzed S-methylation of sulfonyl hydrazides with TBHP was efficiently developed, providing a variety of methyl sulfones with good to excellent yields. The reaction can be carried out in water smoothly without any ligand or additive under mild conditions and this catalyst-in-water can be recycled several times.
- Yang, Yu,Bao, Yajie,Guan, Qianqian,Sun, Qi,Zha, Zhenggen,Wang, Zhiyong
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p. 112 - 116
(2017/08/15)
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- Improved schmidt conversion of aldehydes to nitriles using azidotrimethylsilane in 1,1,1,3,3,3-Hexafluoro-2-Propanol
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The Schmidt reaction of aromatic aldehydes using a substoichiometric amount (40 mol %) of triflic acid is described. Low catalyst loading was enabled by a strong hydrogen-bond-donating solvent hexafluoro-2-propanol (HFIP). This improved protocol tolerates a broad scope of aldehydes with diverse functional groups and the corresponding nitriles were obtained in good to high yields without the need for aqueous work up.
- Motiwala, Hashim F.,Yin, Qin,Aubé, Jeffrey
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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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- Cobalt-Catalyzed Electrophilic Cyanation of Arylzinc Halides with N-Cyano-N-phenyl-p-methylbenzenesulfonamide (NCTS)
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The cobalt-catalyzed cross-coupling of organozinc bromides with N-cyano-N-phenyl-p-methylbenzenesulfonamide (NCTS) is described. The same cobalt catalyst, cobalt(II) bromide, was used for both the synthesis of the organozinc species and the cross-coupling reaction. However in this case, a catalytic amount of zinc dust is necessary in the second step to release the low-valent cobalt. Under these mild conditions, moderate to excellent yields of different benzonitriles were obtained.
- Cai, Yingxiao,Qian, Xin,Rrat, Alice,Auffrant, Audrey,Gosmini, Corinne
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supporting information
p. 3419 - 3423
(2016/01/25)
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- Diaryl-substituted (Dihydro)pyrrolo[3,2,1- hi ]indoles, a class of potent COX-2 inhibitors with tricyclic core structure
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A new compound class of diaryl-substituted heterocycles with tricyclic dihydropyrrolo[3,2,1-hi]indole and pyrrolo[3,2,1-hi]indole core structures has been designed and was synthesized by a modular sequence of Friedel-Crafts acylation, amide formation, and
- Laube, Markus,Gassner, Cemena,Sharma, Sai Kiran,Günther, Robert,Pigorsch, Arne,K?nig, Jonas,K?ckerling, Martin,Wuest, Frank,Pietzsch, Jens,Kniess, Torsten
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p. 5611 - 5624
(2015/06/16)
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- One-pot transformation of methylarenes into aromatic nitriles with inorganic metal-free reagents
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Various methylarenes were transformed into the corresponding aromatic nitriles in good to moderate yields by the treatment with aq. HBr and aq. H 2O2, followed by reaction with molecular iodine and aq. ammonia in a one-pot procedure. The present reaction is a useful, practical, transition-metal-free, and organic-reagent-free method for the preparation of aromatic nitriles from methylarenes. Various methylarenes were treated with aq. HBr and aq. H2O2 under warming conditions and/or irradiation conditions, followed by the reaction with molecular iodine and aq. ammonia, to provide the corresponding aromatic nitriles, in a one-pot procedure. The present reaction was carried out under metal-free and organic-reagent-free conditions. Copyright
- Kawagoe, Yuhsuke,Moriyama, Katsuhiko,Togo, Hideo
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p. 4115 - 4122
(2014/07/08)
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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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- Direct oxidative conversion of methylarenes into aromatic nitriles
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A variety of methylarenes were successfully converted into the corresponding aromatic nitriles in good to moderate yields by the treatment with NBS or DBDMH in the presence of a catalytic amount of AIBN or BPO, followed by the reaction with molecular iodine in aq NH3 in a one-pot procedure. The present reaction is a useful and practical transition-metal-free method for the preparation of aromatic nitriles from methylarenes.
- Tsuchiya, Daisuke,Kawagoe, Yuhsuke,Moriyama, Katsuhiko,Togo, Hideo
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p. 4194 - 4197
(2013/09/12)
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- Asymmetric counteranion-directed iron catalysis: A highly enantioselective sulfoxidation
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A highly active and enantioselective ion-pair sulfoxidation catalyst, consisting of an achiral iron(III)-salen cation and a chiral phosphate counteranion, mediates the oxidization of various sulfides with high yields and enantioselectivities. The enantioselectivities observed, especially for electron-poor substrates, represent the best results so far in manganese and iron-salen systems. This work represents the first application of our concept of asymmetric counteranion-directed catalysis (ACDC) to iron catalysis. Copyright
- Liao, Saihu,List, Benjamin
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supporting information
p. 2363 - 2367
(2012/10/30)
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- Catalyst-free approach for solvent-dependent selective oxidation of organic sulfides with oxone
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Selective oxidation of sulfides was successfully performed by employing oxone (2KHSO5·KHSO4·K2SO 4) as oxidant without utilization of any catalyst/additive under mild reaction conditions. Notably, the reaction can be controlled by the chosen solvent. When ethanol was used as the solvent, sulfoxides were obtained in excellent yield; the reaction almost exclusively gave the sulfone in water. Furthermore, this protocol worked well for various sulfides to the corresponding sulfoxides in ethanol or sulfones in water.
- Yu, Bing,Liu, An-Hua,He, Liang-Nian,Li, Bin,Diao, Zhen-Feng,Li, Yu-Nong
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experimental part
p. 957 - 962
(2012/06/04)
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- Preparation and reactivity of polystyrene-supported iodosylbenzene sulfate: An efficient recyclable oxidizing system
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A new polymer-supported hypervalent iodine reagent, polystyrene-supported iodosylbenzene sulfate (PS-IBS), can be conveniently prepared by the reaction of polystyrene-supported (diacetoxyiodo)benzene (PS-DIB) with sodium bisulfate monohydrate under solvent-free conditions. This new recyclable reagent effects clean and efficient oxidation of a wide range of alcohols and sulfides to the corresponding carbonyl compounds or sulfoxides in high conversions under mild conditions. The final products are conveniently separated from the polymeric byproduct by simple filtration and isolated in good purity after evaporation of solvent. Recycling of the resin is possible with minimal loss of activity after several reoxidations.
- Chen, Jiang-Min,Zeng, Xiao-Mei,Zhdankin, Viktor V.
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experimental part
p. 2771 - 2774
(2010/12/25)
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- Sulfoxidation with hydrogen peroxide catalyzed by [SeO 4{WO(O2)2}2]2-
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The selenium-containing dinuclear peroxotungstate, [(n-C4H 9)4N]2[SeO4{WO(O2) 2}2] (I), acts as a homogeneous catalyst for the selective oxidation of various kinds of cyclic mono- and disulfides with 30% aqueous H2O2. The cyclic disulfides were selectively oxidized to the corresponding monosulfoxides with one equivalent of H2O 2 with respect to the sulfides. In the presence of two equivalents of H2O2, the oxidation of dibenzothiophene gave the corresponding sulfone in 98% yield under the mild conditions. The negative Hammett ρ value (-0.62) for the competitive oxidation of p-substituted thioanisoles and the low XSO (XSO = (nucleophilic oxidation)/(total oxidation)) value of 0.14 for the I-catalyzed oxidation of thianthrene 5-oxide (SSO) revealed that I is a strong electrophilic oxidant. The reactivities of the di- and tetranuclear peroxotungstates with XO 4n- ligands (X = Se(vi), As(v), P(v), S(vi), and Si(iv)) were strongly dependent on the kinds of hetero atoms. The reaction rates for the sulfoxidation decreased with an increase in the XSO values and a peroxotungstate with a stronger electrophilicity was more active for the sulfoxidation. The kinetic and mechanistic investigations showed that the electrophilic attack of the peroxo oxygen at the sulfur atom is a key step in the sulfoxidation. The computational investigation supported the high chemoselectivitiy for the sulfoxidation of diallyl sulfide.
- Kamata, Keigo,Hirano, Tomohisa,Ishimoto, Ryo,Mizuno, Noritaka
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supporting information; experimental part
p. 5509 - 5518
(2010/08/04)
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- Highly efficient oxidation of sulfides with hydrogen peroxide catalyzed by [SeO4{WO(O2)2}2]2-
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By using the selenium-containing dinuclear peroxotungstate at 0.005-0.1 mol%, various kinds of sulfides could be converted into the corresponding sulfoxides or sulfones in excellent yields with one or two equivalents of H 2O2 with respect to the sulfide, respectively.
- Kamata, Keigo,Hirano, Tomohisa,Mizuno, Noritaka
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supporting information; experimental part
p. 3958 - 3960
(2010/01/06)
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- Methods for the use of inhibitors of cytosolic phospholipase A2 in the treatment of thrombosis
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This invention provides methods for the use of substituted indole compounds of the general formula: and pharmaceutically acceptable salt forms thereof. The invention provides methods for the use of the compounds in the treating or preventing thrombosis in a mammal, or preventing progression of symptoms of thrombosis.
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Page/Page column 18
(2010/11/29)
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- An investigation by means of correlation analysis into the mechanisms of oxidation of aryl methyl sulfides and sulfoxides by dimethyldioxirane in various solvents
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Relative rate constants have been measured for the oxidation of aryl methyl sulfides and sulfoxides by dimethyldioxirane in acetone, in mixtures of acetone with aprotic co-solvents of both higher and lower relative permittivity, and in aqueous acetone mixtures. Correlation analyses of the effects of substituents in the different solvents show that, with one exception, reactions take place via a single step mechanism in which the formation of the new SO bond and the elimination of acetone occur concertedly. The exception was oxidation of the sulfides in aqueous acetone containing the highest proportion of water of those studied (20% v/v). Here, the behaviour of the reaction is consistent with a two-step mechanism in which the oxidant reversibly attacks the sulfide to form an open-chain sulfonium betaine that subsequently fragments to sulfoxide and acetone. There is no evidence for the participation of an intermediate dioxathietane as has been found in the case of sulfide oxidations by (trifluoromethyl)methyldioxirane in CH2Cl2 and similar aprotic solvents. It is not justified to generalise a mechanism involving a betaine, with or without a derived dioxathietane, to the reactions of dimethyldioxirane in acetone. This journal is The Royal Society of Chemistry.
- Hanson, Peter,Hendrickx, Ramon A.A.J.,Smith, John R. Lindsay
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p. XX745-761
(2008/09/17)
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- [γ-1,2-H2SiV2W10O40] immobilized on surface-modified SiO2 as a heterogeneous catalyst for liquid-phase oxidation with H2O2
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An organic-inorganic hybrid support has been synthesized by covalently anchoring an N-octyldihydroimidazolium cation fragment onto SiO2 (denoted as 1-SiO2). This modified support was characterized by solid-state 13C, 29Si, and 31P NMR spectroscopy, IR spectroscopy, and elemental analysis. The results showed that the structure of the dihydroimidazolium skeleton is preserved on the surface of SiO2. The modified support can act as a good anion exchanger, which allows the catalytically active polyoxometalate anion [γ-1,2-H 2SiV2W10O40]4- (I) to be immobilized onto the support by a stoichiometric anion exchange (denoted as I/1-SiO2). The structure of anion I is preserved after the anion exchange, as confirmed by IR and 51V NMR spectroscopy. The catalytic performance for the oxidation of olefins and sulfides, with hydrogen peroxide (only one equivalent with respect to substrate) as the sole oxidant, was investigated with I/1-SiO2. This supported catalyst shows a high stereospecificity, diastereoselectivity, regioselectivity, and a high efficiency of hydrogen peroxide utilization for the oxidation of various olefins and sulfides without any loss of the intrinsic catalytic nature of the corresponding homogeneous analogue of I (i.e., the tetra-n-butylammonium salt of I, TBA-I), although the rates decreased to about half that with TBA-I. The oxidation can be stopped immediately by removal of the solid catalyst, and vanadium and tungsten species' can hardly be found in the filtrate after removal of the catalyst. These results rule out any contribution to the observed catalysis from vanadium and tungsten species that leach into the reaction solution, which means that the observed catalysis is truly heterogeneous in nature. In addition, the catalyst is reusable for both epoxidation and sulfoxidation without any loss of catalytic performance.
- Kasai, Jun,Nakagawa, Yoshinao,Uchida, Sayaka,Yamaguchi, Kazuya,Mizuno, Noritaka
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p. 4176 - 4184
(2007/10/03)
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- Asymmetric sulfoxidation of thioethers with hydrogen peroxide in water mediated by platinum chiral catalyst
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Easy stereoselective oxidation of prochiral aryl alkyl sulfides 2 to the corresponding sulfoxides can be achieved in water-surfactant medium with inexpensive hydrogen peroxide mediated by the chiral platinum diphosphine complex {[(R)-BINAP]Pt(μ-OH)}2
- Scarso, Alessandro,Strukul, Giorgio
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p. 1227 - 1234
(2007/10/03)
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- Synthesis of aryl sulfones via L-proline-promoted CuI-catalyzed coupling reaction of aryl halides with sulfinic acid salts
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(Chemical Equation Presented) The CuI/L-proline sodium salt catalyzed coupling reaction of aryl halides with sulfinic acid salts readily occurs at 80-95°C in DMSO to give the corresponding aryl sulfones in good to excellent yields. This process is well-tolerated by a wide range of functional groups including hydroxyl, amino, acetanilide, ketone, ester, and nitrile. Using this method, 4-phenylsulfonyl- and 4-methanesulfonyl-substituted L-phenylalanine derivatives are prepared.
- Zhu, Wei,Ma, Dawei
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p. 2696 - 2700
(2007/10/03)
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- A mild and efficient new synthesis of aryl sulfones from boronic acids and sulfinic acid salts
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A new efficient and mild preparation of sulfones from boronic acids and sulfinic acid salts is reported. The cross-coupling reaction mediated by cupric acetate gives access to a variety of sulfones in excellent yield.
- Beaulieu, Christian,Guay, Daniel,Wang, Zhaoyin,Evans, David A.
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p. 3233 - 3236
(2007/10/03)
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