Glycine ruthenium complexes

Treatment with the nickel(II) complex of the tripeptide glycine-glycine-histidine in the presence of magnesium monoperoxyphthalate Visible light irradiation in the presence of tris(bipyridyl)ruthenium(II) dication and ammonium persulfate Ethylmercury phosphate Fluorescein... 

An important application of oxidation of a C-H bond adjacent to a nitrogen atom is the selective oxidation of amides. This reaction proceeds in the presence of ferf-BuOOH as the oxidant and Ru(II) salts. Thus in the example of Eq. (36), the a-tert-butylperoxy amide of the isoquinoline was obtained, which is an important synthetic intermediate for natural products [138]. This product can be conveniently reacted with a nucleophile in the presence of a Lewis add. Direct trapping of the iminium ion complex by a nudeophile was achieved in the presence of trimethylsilyl cyanide, giving a-cyanated amines as shown in Eq. (37) [45]. This ruthenium/peracid oxidation reaction provides an alternative to the Strecker reaction for the synthesis of a-amino acid derivatives since they involve the same a-cyano amine intermediates. In this way N-methyl-N-(p-methoxyphenyl) glycine could be prepared from N,N-dimethyl-p-methoxyaniline in 82% yield. 

Transition metal complexes, zeolites, biomimetic catelysts have been widely used for various oxidation reactions of industrial and environmental importance [1-3]. However, few heterogenized polymeric catalysts have also been applied for such purpose. Mild condition oxidation catalyzed by polymer anchored complexes is attractive because of reusability and selectivity of such catalysts. Earlier we have reported synthesis of cobalt and ruthenium-glycine complex catalysts and their application in olefin hydrogenation [4-5]. In present study, we report synthesis of the palladium-glycine complex on the surface of the styrene-divinylbenzene copolymer by sequential attachment of glycine and metal ions and investigation of oxidation of toluene to benzaldehyde which has been widely used as fine chemicals as well as an intermidiate in dyes and drugs. 

Schdllkopfs chiral glycine enolate equivalents, as in the elegant synthesis of the central diarylether unit of ristocetin [169]. It is remarkable that these limitations were partly lifted by using, instead of the manganese tricarbonyl complex the corresponding iron or ruthenium cyclopentadienyl complexes [170] (Scheme 62). 

CoX NHj) ] + (X = H20, nitrile, glycine, alanine ) and [Co(en)2(L-L)]"+ (L-L = thiolate, thioether, alkoxy, carboxylate) by [Ru(NH3)6]"+ has been studied kinetically, the specific rates for reduction of the nitrile complexes being increased due to electron withdrawal by the C=N moiety. For the glycine and alanine complexes, no pH dependence was observed, the electron transfer being thought not to occur via coordination of carboxylate to ruthenium. Kinetic studies have also been carried out on the reduction of [Fe(L)(OH2)2] (L = tetra-4-iV-methylpyridyl por-phine), [Fe(edta)] , cytochrome aa3, cytochrome c(III), platinum(IV) and copper(ll)/ complexes and perchlorate salts.The reduction of Fe " is found to be faster than that of [FeOHf. The importance of non-adiabaticity in the above outer-space mechanisms has been discussed. ... 

Fig. 12 Carbon monoxide releasing compounds a manganese decacarbonjd b tricar-bonjdruthenium chloride dimer c a ruthenium-glycinate complex d iron carbonyl nucleoside analogues, TDSO = thex)4dimeth)4sil)4oxy...

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