Ruthenium sulfur oxidation with

A ruthenium(lV) complex with six sulfur donor atoms, [Ru (mnt)3] (143), is formed by oxidation of [Ru (mnt)3] (mnt = 1,2-dicyanoethylene dithiolate) with I2, H2O2, or Ce. The complex is paramagnetic with a magnetic moment of 2.84 The Ru—5 distances range from... 

Deacetylation of 80 in methanolic sodium methoxide and successive O-isopropyli-denation with 2,2-dimethoxypropane gave 2-0-acetyl-3,4-O-isopropylidene-l,6-an-hydro-pseudo-p-DL-galactopyranose (81), after acetylation. Removal of the acetyl group of 81, followed by oxidation with ruthenium tetroxide and sodium metaperiodate afforded the 2-oxo derivative (82). Catalytic hydrogenation of 82 under the presence of platinum catalyst and acetolysis in a mixture of acetic acid, acetic anhydride and sulfuric acid gave pseudo-P-DL-talopyranose pentaacetate (83) [25] (Scheme 17). 

Cyclic sulfates provide a useful alternative to epoxides now that it is viable to produce a chiral diol from an alkene. These cyclic compounds are prepared by reaction of the diol with thionyl chloride, followed by ruthenium-catalyzed oxidation of the sulfur (Scheme 9.26).166 This oxidation has the advantage over previous procedures because it only uses a small amount of the transition metal catalyst.167168... 

A powerful oxidizer and very reactive material. It has been the cause of many industrial explosions. May explode on heating. Explosive reactions with ammonium chloride, aqua regia + ruthenium, sulfur dioxide solutions in ether or ethanol. Reacts with fluorine to form the explosive gas fluorine perchlorate. 

Electrochemical oxidation catalysts with ruthenium centers are the basis of several amperometric detectors that permit determination of a variety of biochemical compounds at the sub-micromolar level in flow systems. Modification of glassy carbon electrodes with films of mvRuOx is particularly useful for peptides that contain sulfur. Oxidation to polar products that are not adsorbed on the electrode occurs by concurrent oxygen and electron transfer. These electrodes have longterm stability as long as the analytes are at concentrations below about 10 pM. 

L.G. Shaidarova, S.A. Ziganshina, L.N. Tikhonova, and G.K. Budnikov, Electrocatalytic oxidation and flow-injection determination of sulfur-containing amino acids at graphite electrodes modified with a ruthenium hexacyanoferrate film. J. Anal. Chem. 58, 1144-1150 (2003). 

Ruthenium(III) catalyses the oxidative decarboxylation of butanoic and 2-methylpropanoic acid in aqueous sulfuric acid. ° Studies of alkaline earth (Ba, Sr) metal alkoxides in amide ethanolysis and of alkali metal alkoxide clusters as highly effective transesterification catalysts were covered earlier. Kinetic studies of the ethanolysis of 5-nitroquinol-8-yl benzoate (228) in the presence of lithium, sodium, or potassium ethoxide revealed that the highest catalytic activity is observed with Na+.iio... 

The impressive activity achieved by Teles catalyst was improved some years later by the use of CO as an additive [92]. In this study, Hayashi and Tanaka reported a TOF of 15600h 1, at least two orders of magnitude higher than [as-PtCl2(tppts)2], for the hydration of alkynes, providing an alternative synthetic route to the Wacker oxidation. Although several solvents were tested, the best results were obtained with aqueous methanol, and sulfuric acid or HTfO as acidic promoters. Unlike Utimoto s observation, in this case terminal propargylic alcohols partially (17-20%) delivered anti-Markovnikov product, in addition to the Markovnikov species. Some years before, Wakatsuki et al. had already reported the anti-Markovnikov hydration of terminal alkynes catalyzed by ruthenium(II) [93]. 

Ethers in which at least one group is primary alkyl can be oxidized to the corresponding carboxylic esters in high yields with ruthenium tetroxide.297 Cyclic ethers give lactones. The reaction, a special case of 9-16, has also been accomplished with CrO, in sulfuric acid.39" with benzyltriethylammonium permanganate,299 and with trichloroisocyanuric acid in the presence of an excess of water.300 In a similar reaction, cyclic tertiary amines (e.g., 28) can... 

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