1193-82-4Relevant articles and documents
Template Effects of a Clay-Chelate Adduct on the Asymmetric Oxidation of Alkyl Phenyl Sulphide by Sodium Metaperiodate
Yamagishi, Akihiko
, p. 290 - 291 (1986)
Cyclohexyl phenyl sulphide adsorbed by Δ-tris(1,10-phenanthroline)nickel(II)-montmorillonite was oxidized by sodium metaperiodate at 25 deg C in water to give (S)-cyclohexyl phenyl sulphoxide with an optical purity of 78percent.
Rates and mechanism of the stoichiometric oxidations of organic sulphides to sulphoxides with the peroxomolybdenum complex MoO(O2)2HMPT
Ballistreri, Francesco Paolo,Failla, Salvatore,Spina, Emanuela,Tomaselli, Gaetano Andrea
, p. 39 - 44 (1989)
Stoichiometric oxidations of various organic sulfides were performed in 1,2-dichloroethane at -15°C with the oxodiperoxocomplex MoO(O2)2-HMPT in the absence and in the presence of Hg(OCOCF3)2. The oxidation cata
Nitrogen donor-controlled chemoselectivity of reaction in oxidation of sulfides with tetra-n-butylammonium hydrogen monopersulfate catalyzed by a partially β-brominated meso-tetraphenylporphyrinatomanganese(III) acetate: A clue to the nature of active oxidant
Rayati, Saeed,Zakavi, Saeed,Noroozi, Vahid
, p. 89 - 95 (2010)
Highly efficient and rapid oxidation of different sulfides to the corresponding sulfones with tetra-n- butylammonium hydrogen monopersulfate (TBAO) in the presence of catalytic amounts of Mn(TPPBr2)OAc at room temperature is reported. Contrary to other nitrogen donors, using 4-cyanopyridine as co-catalyst leads to an increase in the ratio of sulfoxide to sulfone in the products. Comparison of the chemoselectivity of reaction in the presence of different nitrogen donors as co-catalyst shows the involvement of a high-valent Mn-oxo species as well as the six-coordinate Mn(TPPBr2)(HSO5)(B) (B = nitrogen donors) complex in sulfide oxidation reactions with TBAO.
Effects of the environment on microperoxidase-11 and on its catalytic activity in oxidation of organic sulfides to sulfoxides
Kadnikova, Ekaterina N.,Kostic, Nenad M.
, p. 2600 - 2608 (2003)
Microperoxidase-11 (MP-11, also known as heme undecapeptide of cytochrome c) was immobilized by encapsulation into sol-gel silica glass and by physisorption, chemisorption, and covalent attachment to silica gel. We then compared these species with one ano
A mononuclear nonheme cobalt(III)-hydroperoxide complex with an amphoteric reactivity in electrophilic and nucleophilic oxidative reactions
Tcho, Woon-Young,Wang, Bin,Lee, Yong-Min,Cho, Kyung-Bin,Shearer, Jason,Nam, Wonwoo
, p. 14511 - 14515 (2016)
A mononuclear nonheme cobalt(iii)-hydroperoxide complex bearing a tetramethylated cyclam ligand, [(12-TMC)CoIII(OOH)]2+, was synthesized and characterized spectroscopically and computationally; the cobalt(iii)-hydroperoxide complex exhibited an amphoteric reactivity in electrophilic and nucleophilic oxidative reactions.
Catalytic Asymmetric Oxidation of Sulfides to Sulfoxides with tert-Butyl Hydroperoxide Using Binaphthol as a Chiral Auxiliary
Komatsu, Naoki,Hashizume, Masaya,Sugita, Toshio,Uemura, Sakae
, p. 4529 - 4533 (1993)
The asymmetric oxidation of sulfides to chiral sulfoxides in moderate yield with tert-butyl hydroperoxide (TBHP) was catalyzed very effectively by a titanium complex produced in situ from a titanium alkoxide and a chiral binaphthol.The highest enantioselectivities (up to 96percent ee) were obtained with commercial aqueous 70percent TBHP under atmospheric conditions at 25 deg C with 2.5 mol percent of the catalyst.The presence of more than 1.0 mol equiv of water relative to sulfide was essential for the oxidation, and it was found that the water was necessary not only to produce an effective catalyst for the highly enantioselective oxidation but also to maintain the catalytic activity of the titanium-binaphthol complex for a longer time.The nature of the solvent had a remarkable effect upon the ee of the sulfoxide.Carbon tetrachloride was proven to be the solvent of choice; the use of other chlorinated solvents resulted in low enantioselectivity.A moderate level of asymmetric amplification was observed in this catalytic system.From a mechanistic standpoint, it was revealed that the initial asymmetric oxidation to the chiral sulfoxide (ca. 50percent ee) is followed by the kinetic resolution of the sulfoxide; that is, the titanium-binaphthol complex catalyzes not only the asymmetric oxidation but also the subsequent kinetic resolution.
Do trinuclear triplesalen complexes exhibit cooperative effects? Synthesis, characterization, and enantioselective catalytic sulfoxidation by chiral trinuclear FeIII triplesalen complexes
Mukherjee, Chandan,Stammler, Anja,Boegge, Hartmut,Glaser, Thorsten
, p. 10137 - 10149 (2010)
The chiral triplesalen ligand H6chand provides three chiral salen ligand compartments in a meta-phenylene arrangement by a phloroglucinol backbone. The two diastereomeric versions H6chand RR and H 6chand rac have been used to synthesize the enantiomerically pure chiral complex [(FeCl)3-(chand RR)] (3 RR) and the racemic complex [(FeCl)3(chand rac)] (3 rac). The molecular structure of the free ligand H6chand rac exhibits at the terminal donor sides the O-protonated phenol-imine tautomer and at the central donor sides the N-protonated keto-enamine tautomer. The trinuclear complexes are comprised of five-coordinate square-pyramidal Fe III ions with a chloride at the axial positions. The crystal structure of 3 rac exhibits collinear chiral channels of ～11 A in diameter making up 33.6 % of the volume of the crystals, whereas the crystal structure of 3 RR exhibits voids of 560 A 3. Moessbauer spectroscopy demonstrates the presence of Fe III high-spin ions. UV/Vis spectroscopy is in accordance with a large delocalized system in the central backbone evidenced by strong low-energy shifts of the imine π-π * transitions relative to that of the terminal units. Magnetic measurements reveal weak intramolecular exchange interactions but strong magnetic anisotropies of the Fe III ions. Complexes 3 rac and 3 RR are good catalysts for the sulfoxidation of sulfides providing very good yields and high selectivities with 3 RR being enantioselective. A comparison of 3 RR and [FeCl-(salen')] provides higher yields and selectivities but lower enantiomeric excess values (ee values) for 3 RR relative to [FeCl(salen')]. The low ee values of 3 RR appeared to be connected to a strong ligand folding in 3 RR, opening access to the catalytically active high-valent Fe-O species. The higher selectivity is assigned to a cooperative stabilization of the catalytically active high-valent Fe-O species through the phloroglucinol backbone in the trinuclear complexes.
Ni(II) and V(IV) Schiff base complexes derived from 2,2′-dimethylpropandiamine: the crystal structure, electrochemical properties and catalytic activities in oxidation of sulfides
Rayati, Saeed,Khodaei, Elham,Jafarian, Majid,Bahrami, Arezo,Wojtczak, Andrzej,Kozakiewicz, Anna
, p. 1424 - 1437 (2017)
Tetradentate Schiff base (H2L) derived from 2,2′-dimethylpropandiamine and its nickel(II) and oxo-vanadium(IV) complexes (NiL, VOL) have been prepared and characterized. The crystal structure of NiL has been determined. The reported structure c
Synthesis, structural studies, and oxidation catalysis of the late-first-row-transition-metal complexes of a 2-pyridylmethyl pendant-armed ethylene cross-bridged cyclam
Jones, Donald G.,Wilson, Kevin R.,Cannon-Smith, Desiray J.,Shircliff, Anthony D.,Zhang, Zhan,Chen, Zhuqi,Prior, Timothy J.,Yin, Guochuan,Hubin, Timothy J.
, p. 2221 - 2234 (2015)
The first 2-pyridylmethyl pendant-armed ethylene cross-bridged cyclam ligand has been synthesized and successfully complexed to Mn2+, Fe2+, Co2+, Ni2+, Cu2+, and Zn2+ cations. X-ray crystal structures were obtained for all six complexes and demonstrate pentadentate binding of the ligand with the requisite cis-V configuration of the cross-bridged cyclam ring in all cases, leaving a potential labile binding site cis to the pyridine donor for interaction of the complex with oxidants and/or substrates. The electronic properties of the complexes were evaluated using solid-state magnetic moment determination and acetonitrile solution electronic spectroscopy, which both agree with the crystal structure determination of high-spin divalent metal complexes in all cases. Cyclic voltammetry in acetonitrile revealed reversible redox processes in all but the Ni2+ complex, suggesting that catalytic reactivity involving electron-transfer processes is possible for complexes of this ligand. Kinetic studies of the dissociation of the ligand from the copper(II) complex under strongly acidic conditions and elevated temperatures revealed that the pyridine pendant arm actually destabilizes the complex compared to the parent cross-bridged cyclam complex. Screening for oxidation catalysis using hydrogen peroxide as the terminal oxidant for the most biologically relevant Mn2+, Fe2+, and Cu2+ complexes identified the Mn2+ complex as a potential mild oxidation catalyst worthy of continued development.
Direct evidence for oxygen-atom exchange between nonheme oxoiron(IV) complexes and isotopically labeled water
Seo, Mi Sook,In, Jun-Hee,Kim, Sun Ok,Oh, Na Young,Hong, Jongki,Kim, Jinheung,Que Jr., Lawrence,Nam, Wonwoo
, p. 2417 - 2420 (2004)
Rates of exchange: Evidence that non-heme oxoiron(IV) complexes exchange their oxygen atoms with H218O was obtained for the first time, by monitoring electrospray ionization mass spectral changes of the oxoiron(IV) species. The oxyge
