Silver complexes amino acids

When side chains containing alkenic groups were introduced, it was found that the stability was generally higher than in amino adds having fully saturated side chains. Interaction of the silver ion with the alkene was proposed to account for this increase in stability. 00 Thermodynamic data for the formation of some silver(I) amino acid complexes are collected in Table 54.398 04,411... 

Hayama et al.132 discussed the catalytic effects of silver ion-polyacrylic add systems toward the hydrolyses of 2,4-dinitrophenylvinylacetate 84 (DNPVA) by using the weak nudeophilicity of carboxylic groups and the change-transfer interactions between olefinie esters and silver ions133Metal complexes of basic polyelectrolytes are also stimulating as esterase models. Hatano etal. 34, 13S) reported that some copper(II)-poly-L-lysine complexes were active for the hydrolyses of amino acid esters, such as D- and L-phenylalanine methyl ester 85 (PAM). They... 

Uptake of small organic metal complexes over transport systems of organic metabolites may be possible, for example, of small organic acids like citrate or amino acids. However, only few examples of such processes have been studied so far. Increased uptake of cadmium by an alga has been observed in the presence of citrate and has been attributed to accidental transport of the metal-citrate complex over a citrate transporter [212]. Transport systems of inorganic anions may also play a role in metal transport. Silver uptake by algae was enhanced in the presence of thiosulfate. In this case, the silver thiosulfate complex was transported over a sulfate uptake system [213]. It remains to be demonstrated how widespread these processes may be for metal uptake in the aquatic environment [12]. 

As the result of hydrolysis a complex mixture of all, or nearly all, the previously mentioned units is obtained. These have been isolated by various methods based upon the fractional crystallisation of the compounds themselves, or of their copper, silver and other salts. Only when one or more of the amino acids occurred in somewhat large amounts was their isolation and characterisation effected their amount seldom reached a value higher than 20 per cent, of the total quantity and the remainder was represented by uncrystallisable syrups of unknown nature. A great advance was made when Drechsel discovered that the protein molecule contained diamino acids as well as monoamino acids, and to Kossel and Kutscher we owe our chief knowledge concerning their isolation and estimation. Emil Fischer, in igoi, by his... 

The reaction of silver(I) ions with amino acids has received considerable attention.397 A number of studies have attempted to analyze the effects of substituents on the stability of the silver(I) complexes. When a series of a>-amino adds NHJ(CH2) C02 (n = 1-5) were examined, it was found that lengthening of the aliphatic side chain increased the overall stability of the complex.398,399... 

The oxidative effects of silver(II) complexes of pyridine carboxylates have been studied for a variety of substrates. With ar-amino acids, a rapid reaction occurred at 70 °C in aqueous solution with bis(pyridyl-2-carboxylato)silver(II). 4 The product was the next lower homologous aldehyde and yields were generally greater than 80%. Other substrates included primary and secondary amines, alcohols, monosaccharide derivatives, alkenes, arylalkanes and arylalkanols.90 Only minor differences were detected in efficiencies when 2-, 3- or 4-mono-, or 2,3-di-carboxylates were used as the oxidant. 

The deposition of silver in tissues is the result of the precipitation of insoluble silver salts, such as silver chloride and silver phosphate. These insoluble silver salts appear to be transformed into soluble silver sulfide albuminates, to bind to or form complexes with amino or carboxyl groups in RNA, DNA, and proteins, or to be reduced to metallic silver by ascorbic acid or catecholamines (Danscher 1981). The blue or gray discoloration of skin exposed to ultraviolet light in humans with argyria may be caused by the photoreduction of silver chloride to metallic silver. The metallic silver is then oxidized by tissue and bound as black silver sulfide (Danscher 1981). Bucklet et al. (1965) identified silver particles deposited in the dermis of a woman with localized argyria as being composed of silver sulfide. 

In the case of inert cobalt(m) complexes it is possible to isolate the chelated products of the reaction. Let us return to the hydrolysis of the complex cations [Co(en)2(H2NCH2C02R)Cl]2+ (3.1), which contain a monodentate iV-bonded amino acid ester, that we encountered in Fig. 3-8. The chelate effect would be expected to favour the conversion of this to the chelated didentate AO-bonded ligand. However, the cobalt(iu) centre is kinetically inert and the chloride ligand is non-labile. When silver(i)... 

In contrast, the Hoveyda and Snapper groups reported the efficient catalysis of silver acetate complexes of imine 204.86 These authors first established the superior performance of IV-ort/zo-methoxyaniline-substituted imines in the reaction with Danishefsky diene 195. Because of the modular nature of ligand 206, optimization of its structure could be achieved by surveying a combinatorial library of amino acid derivatives. The /-isoleucine para-methoxyaniline conjugate 206 proved the best. This ligand facilitated full conversion within 2-3 h with high yield and enantioselectivity (Scheme 2.53). 

Hoveyda and coworkers reported that the silver complex generated from AgF2 and an amino acid-based ligand could be used for the asymmetric aldol reaction with silyl enol ethers and a-ketoesters (Table 9.11).23... 

The use of Lewis acid drastically changes the regioselectivity. The highly enantioselective and O-selective nitroso aldol reactions of tin enolates with nitrosobenzene have been developed with the use of (i )-BINAP-silver complexes as catalysts. AgOTf and AgCICL complexes are optimal in the O-selective nitroso aldol reaction in both asymmetric induction (up to 97% ee) and regioselection (0/N= > 99/1), affording amino-oxy ketone. The product can be transformed to a-hydroxy ketone without any loss of enantioselectivity (Equation (71)).224... 

Belokon et al. have published a somewhat intricate protocol for the N -methylation of a histidine isomer, itself an imidazolium derivatised a-amino acid [158] (see Chapter 6). The amino group can be N-boc protected and the resulting imidazolium salt reacted with silver(I) oxide to yield the corresponding silver(l) carbene complex. The functional groups in the wingtip group... 

Figure 3.56 The silver complex of an N-boc protected imidazolium derivatised a-amino acid.

It was thought originally that in these complexes, the main bond was that formed between the copper atom and the carboxylate ion, the bonds existing with the amino group being auxiliary. It is now considered, however, that all the bonds, whether to oxygen or nitrogen atoms, are identical. This is evident since the reaction of the silver salts of the amino acids with alkyl halides results in the formation not only of the ester but also of the N-alkyl compound,... 

This BINAP silver(I) complex was subsequently used by Lectka and coworkers as a catalyst for Mannich-type reactions [35]. Slow addition of silyl enol ether 49 to a solution of tosylated a-imino ester 80 under the influence of 10 mol % (i )-BINAP AgSbFg at -80 °C affords the corresponding amino acid derivative 81 in 95 % yield with 90 % ee (Sch. 20). They reported, however, that (R)-Tol-BINAP-CuC104-(CH3CN)2 was a more effective chiral Lewis acid for the reaction and gave the highest yield and ee at 0 °C. 

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