Stoffwechselprodukte von Mikroorganismen. 174. Mitteilung Eine neue Synthese des Ferrichroms; enantio‐Ferrichrom

Abstract

Metabolites of Microorganisms. A New Synthesis of Ferrichrome; enantio‐Ferrichrome The enantiomer of the natural sideramine ferrichrome was synthesized starting from D‐ornithine. The cyclohexapeptide (D‐Orn)3‐Gly3 was obtained by conventional methods of polypeptide chemistry. For the oxidation of the δ‐amino groups of the D‐ornithine residues to hydroxylamino groups the oxaziridine pathway was successful. The final steps ‐ introduction of the acetyl groups and formation of the iron trihydroxamate complex ‐ followed known procedures. The spectroscopic and chromatographic properties of the crystalline product corresponded to those of natural ferrichrome, the optical rotations and CD. curves being opposite. The biological activity of enantio‐ferrichrome was similar to that of the natural sideramine.

Peptide siderophores

“…The research on clinically useful, especially orally applicable, chelators extends into the field of synthetic compounds [168,169], for which siderophores and their complexation mechanisms can serve as lead structures for drug development. The synthetic methods of peptide chemistry not only serve to verify structural results, but also provide access to a large number of analogues [147, 170±172] and stereochemical counterparts [148,173]. With these analogues, it is possible to study the complexation kinetics and equilibria, the structure of complexes, the structural prerequisites for metal complexation and the extent of receptor specificity.…”

Comprehensive Spectroscopic, Steady State, and Transient Kinetic Studies of a Representative Siderophore-associated Flavin Monooxygenase

“…The synthesis of N 5 -hydroxy-L-ornithine (L-Orn-OH) followed an indirect heteroatom oxidation method starting from commercially available ␣-N-benzyloxycarbonyl-L-ornithine, 1 (supplemental Scheme S1) (48,(51)(52)(53). Because full spectroscopic characterization of L-Orn-OH has not been reported, it was isolated and fully characterized as the dihydrobromide salt, 6, and the corresponding monohydrobromide salt, 7 (54,55).…”

Microbial Siderophores

“…Ferrichrome (as do also at least the members of the group for which structural data are available ((366) and references noted in Table 1) shows L-, synthetic enantio-ferrichrome based on D-Orn D-configuration (253). Uptake studies performed with Ustilago sphaerogena (103) using 59 Fe 3+ and [ 14 C]-ferrichrome under optimal conditions (30 C, pH 7) showed rapid resorption of both labels during the first 30 min.…”