Sulfur-containing reductants

Gold(III) and platinum(IV) complexes act as oxidants towards a number of substrates and can be reduced by sulfur-containing reductants. At the beginning of this century Herrmann established that alkyl sulfides reduce gold(III) chloride with formation of the gold(l) derivatives, [AuC1(SR2)]. Today, these well-documented reactions are carried out in aqueous or alcoholic solution, Eq. 9.29  

Thiourea acts as a mild reductant (E° = 0.427 V) for transition metal complexes and is oxidized to formamidine disulfide. Thiourea is an excellent ligand for many metal ions, especially for those of the platinum metals.88 Therefore, in most of its redox reactions, thiourea acts simultaneously as a reductant and as a ligand. For example, OSO4 reacts with thiourea in sulfuric acid to form [Osfthiole] and formamidine disulfide.89 Addition of [NH4][Tc04] to a solution of thiourea in a mixture of ethanol and hydrochloric acid results in the formation of the homoleptic thiourea complex of technetium(in), [Tc(thio)6] . An X-ray structure study of the isolated product, [Tc(thio)6]Cl3-4H20, has shown that the six thiourea ligands are S-bonded to the metal. 

Freeman and coworkers f have reported the reduction of H[AuCU] in aqueous solution by thiourea which yields the gold(I) complex, [Au(thio)2]Cl. Kukushkin, Vorobev-Desyatovskii and Patrabansh have investigated the reactions of the cis and trans isomers of [PtCl4(amine)2] (amine = NH3, 

py) with an excess of thiourea in addic aqueous solutions. In these reactions thiourea plays both the role of reductant and of a ligand. With the CIS isomers of [PtCl4(amine)2], thiourea forms the greenish-yellow complex, [Pt(thio)4]Cl2, and with the trans isomers, the colorless complexes, trans-[Pt(amine)2(thio)2]Cl2, are formed. Thus, the reaction of thiourea92 with isomeric complexes of the type, [PtCl4(amine)2], may be used to determine the geometry. 

The complex, [Bu4N][TcO(L 2] (H2L = 2-aminobenzenethiol), is formed in a similar manner.94 

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Krasotkina J, T Walters, KA Maruya, SW Ragsdale (2001) Characterization of the Bjj- and iron-sulfur-containing reductive dehalogenase from Desulfitobacterium chlororespirans. J Biol Chem 276 40991-40997. 

The differences in the amino acid chemistry of the hide coUagen and the hair keratin are the basis of the lime-sulfide unhairing system. Hair contains the amino acid cystine. This sulfur-containing amino acid cross-links the polypeptide chains of mature hair proteins. In modem production of bovine leathers the quantity of sulfide, as Na2S or NaSH, is normally 2—4% based on the weight of the hides. The lime is essentially an unhmited supply of alkah buffered to pH 12—12.5. The sulfide breaks the polypeptide S—S cross-links by reduction. Unhairing without sulfide may take several days or weeks. The keratin can be easily hydrolyzed once there is a breakdown in the hair fiber stmcture and the hair can be removed mechanically. The coUagen hydrolysis is not affected by the presence of the sulfides (1—4,7). 

The basic seed processing plant design is based on 70% removal of the sulfur contained in the coal used (Montana Rosebud), which satisfies NSPS requirements. Virtually complete sulfur removal appears to be feasible and can be considered as a design alternative to minimize potential corrosion problems related to sulfur in the gas. The estimated reduction in plant performance for complete removal is on the order of 1/4 percentage point. The size of the seed processing plant would have to be increased by roughly 40% but the corresponding additional cost appears tolerable. The constmction time for the 500 MW plant is estimated to be ca five years. 

Sulfur Dioxide Reductant. The Mathieson process uses sulfur dioxide, sodium chlorate, and sulfuric acid to produce chlorine dioxide gas with a much lower chlorine content. The sulfur dioxide gas reductant is oxidized to make sulfuric acid, reducing the overall acid requirement of the process. Air is used to dilute the chlorine dioxide produced by this process. The exit gases flow through a scmbber to which chlorate is added in order to remove any unreacted sulfur dioxide. Spent Hquor, containing some unreacted chlorate, sulfuric acid, and sodium sulfate, continuously overflows from this process. 

Contents Introduction and Principles. - The Reaction of Dichlorocarbene With Olefins. - Reactions of Dichlorocarbene With Non-Olefinic Substrates. -Dibromocarbene and Other Carbenes. - Synthesis of Ethers. - Synthesis of Esters. - Reactions of Cyanide Ion. - Reactions of Superoxide Ions. - Reactions of Other Nucleophiles. - Alkylation Reactions. - Oxidation Reactions. - Reduction Techniques. - Preparation and Reactions of Sulfur Containing Substrates. -Ylids. - Altered Reactivity. - Addendum Recent Developments in Phase Transfer Catalysis. 

Cephachlor (35) became accessible when methods for the preparation of C-3 methylenecephalosporins became convenient. The allylic C-3-acetoxyl residue characteristic of the natural cephalosporins is activated toward displacement by a number of oxygen- and sulfur-containing nucleophiles. Molecules such as can therefore be prepared readily. Subsequent reduction with chromium(II) salts leads to the desired C-3... 

The exact mechanisms of the Raney nickel reactions are still in doubt, though they are probably of the free radical type. It has been shown that reduction of thiophene proceeds through butadiene and butene, not through 1-butanethiol or other sulfur compounds, that is, the sulfur is removed before the double bonds are reduced. This was demonstrated by isolation of the alkenes and the failure to isolate any potential sulfur-containing intermediates. 

Component B is a monomeric reductase with a molecular weight of 35,000 and contains per mol of enzyme, 1 mol of FMN, 2.1 mol of Fe, and 1.7 mol of labile sulfur. After reduction with NADH, the ESR spectrum showed signals that were attributed to a [2Fe-2S] structure and a flavo-semiquinone radical (Schweizer et al. 1987). The molecular and kinetic properties of the enzyme are broadly similar to the Class IB reductases of benzoate 1,2-dioxygenase and 4-methoxybenzoate monooxygenase-O-demethylase. 

On the other hand, one of the first chiral sulfur-containing ligands employed in the asymmetric transfer hydrogenation of ketones was introduced by Noyori el al Thus, the use of A-tosyl-l,2-diphenylethylenediamine (TsDPEN) in combination with ruthenium for the reduction of various aromatic ketones in the presence of i-PrOH as the hydrogen donor, allowed the corresponding alcohols to be obtained in both excellent yields and enantioselectivities, as... 

Other S/N ligands have been investigated in the enantioselective catalytic reduction of ketones with borane. Thus, Mehler and Martens have reported the synthesis of sulfur-containing ligands based on the L-methionine skeleton and their subsequent application as new chiral catalysts for the borane reduction of ketones." The in situ formed chiral oxazaborolidine catalyst has been used in the reduction of aryl ketones, providing the corresponding alcohols in nearly quantitative yields and high enantioselectivities of up to 99% ee, as shown in Scheme 10.60. 

Organic solvents or mixtures of water and solvents such as acetone or water-acetone are commonly used to extract chemicals from sediment samples as for upland soil. An analysis of sediment, collected from waterways or extremely low Eh paddies, frequently requires the removal of sulfur-containing species, although there is little interference from sulfur if the sediments are in a not very reductive condition. Reduced copper and silver nitrate columns are usually used for the removal, but these procedures are not always successful. Recovery studies could be needed to confirm an interference with sulfur. 

MgS04 as stabilizers, and are non-selective in degrading also cellulose and hemicelluloses, while the reductant 820/ is more selective but less effective, and generates various sulfur-containing chemicals including thiosulfate that is corrosive to paper machines (3). 

The beneficial effect of added phosphine on the chemo- and stereoselectivity of the Sn2 substitution of propargyl oxiranes is demonstrated in the reaction of substrate 27 with lithium dimethylcyanocuprate in diethyl ether (Scheme 2.9). In the absence of the phosphine ligand, reduction of the substrate prevailed and attempts to shift the product ratio in favor of 29 by addition of methyl iodide (which should alkylate the presumable intermediate 24 [8k]) had almost no effect. In contrast, the desired substitution product 29 was formed with good chemo- and anti-stereoselectivity when tri-n-butylphosphine was present in the reaction mixture [25, 31]. Interestingly, this effect is strongly solvent dependent, since a complex product mixture was formed when THF was used instead of diethyl ether. With sulfur-containing copper sources such as copper bromide-dimethyl sulfide complex or copper 2-thiophenecarboxylate, however, addition of the phosphine caused the opposite effect, i.e. exclusive formation of the reduced allene 28. Hence the course and outcome of the SN2 substitution show a rather complex dependence on the reaction partners and conditions, which needs to be further elucidated. 

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