Threonine metal complexes

A group at the Academy of Sciences in Moscow 197) has synthesized chiral threonine. Derivatives of cyclic imino acids form copper complexes with glacine and carbonyl compounds. Hydroxyethylation with acetaldehyde and decomposition of the resulting complexes produced threonine with an optical purity of up to 97-100% and with threo/allo ratios of up to 19 1 197). The chiral reagents could be recovered and re-used without loss of stereoselectivity. The mechanism of this asymmetric synthesis of amino acids via glacine Schiff base/metal complexes was also discussed 197). 

Vanadyl and copper(n) ions catalyse the /J-elimination reaction of O-phospho-threonine in the presence of pyridoxal.429 Equilibrium spectroscopic studies of the threonine-metal ion-pyridoxal system have identified a metal-ion complex of the amino-acid-pyridoxal Schiff base. The catalytic effect of the metal is ascribed to its electron-with drawing effecCIt was suggested that the specific catalytic effect of Cu2 + and V02+ arises from their reluctance to co-ordinate the phosphate in an axial position. Other metal ions such as nickel can also form the Schiff base complex but probably stabilize the phosphothreonine system by chelate formation. 

Decomposition of the copper complex with HjS in acid leads to allothreonine and (in about 2-fold excess) threonine. Following the pioneering work of Akabori et this reaction has been extended to a variety of metals and aldehydes and to complexes such as A- and A-Co(en)2gly with intriguing stereoselectivity behavior (optically-active allothreonine and threonine products). ... 

The hydroxy a-amino acids l-serine and l-threonine, used as models for the 2-amino-2-deoxy glyconic acids, have been complexed with Ni(II) at 37 °C in aqueous solutions of 0.15M potassium nitrate. Values for the stability constants were obtained from iso-pH titration data which were collected by alternate, small, incremental additions of metal ion and potassium hydroxide being made such that the pH of the solution remained nearly constant. The data were consistent with the predominance of MLn species, along with additional protonated and hydrolyzed complexes. There was no evidence for the involvement of the hydroxyl group in chelation. By the same iterative computations the complexes formed between borate and mannitol have been analyzed, and the stability constants have been calculated. Complexes with mannitohborate stoichiometries of I.T, 1 2, 1 3, and 2 1 were proposed. 

One of the first reactions reported on the activation of the a C—H bond was the aldol condensation reaction of glycine, coordinated to Cu11, with acetaldehyde to yield threonine.72 The reaction, which is base catalyzed, proceeds under far milder conditions than for free glycine. Similar reactions have been reported with other metal ions and aldehydes again the postulated intermediate is a carbanion.69 70 By using resolved Co111 complexes, e.g. A-(+)-[Co(en)2(GlyO)]2+, some stereoselectivity can be obtained in the threonine product.73... 

Threonine and allothreonine are thermally unstable amino acids. The same is true for the simplest hydroxy amino add, (S)-serine (39). High levels of this amino add have however been reported from certain petroleum brine waters and its preservation may be due to the formation of stable chelates. Ahrens has suggested that metal-amino acid chelates may be important in the sedimentary cycle, and the uptake of certain metals in sediments, particularly in binding of metal-amino acid chelates to clays, has been proposed as a possible mechanism for the incorporation of metal ions in carbonaceous materials. Similar complexes are thought to contribute to the stabilization of amino acids in coals, lignites and peats, but, as has been outlined in a previous section, many other ligands are also present in these media, and their relative importance is difScult to assess. Much of this work is unfortunately of a speculative nature since no well-characterized complex of an amino acid has been isolated from a geological source, as far as the author is aware. 

Catalysis of the hydrolysis of O-phosphoryl threonine in the presence of pyridoxal is observed with Cu and but not with other transition-metal ions there is further rate enhancement when an organic base is added.It seems clear that these two metal ions form a 1 1 complex (21) with the... 

Previous studies have reported silver staining with other amino acids. Heukeshoven and Dernick reported silver staining of the homopolymers of glycine, serine, proline and aspartic acid (4 ) while Nielsen and Brown reported the formation of colored silver complexes with aspartate, and tyrosine (45,). Staining of these homopolymers was not observed in the study of Merril and Pratt (32,), and prior metal binding studies failed to demonstrate metal interactions with the side-chain hydroxyl groups of serine, threonine or tyrosine... 

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