Diaminosuberic acid

Macrocyclization of esters of allylglycine with diols has been successfully used to prepare derivatives of 2,7-diaminosuberic acid [861,864]. The latter are surrogates of cystine, and therefore of interest for the preparation of peptide mimetics. For unknown reasons protected allylglycine derivatives can not be directly dimerized by self metathesis [864]. However, catechol [864], ethylene glycol [861], and 1,2- or 1,3-di(hydroxymethyl)benzene derivatives [860] of allylglycine are suitable templates for the formal self metathesis of this amino acid via RCM. 

The constituent amino acid of dicarba-analogues of cystine is L,L-2,7-diaminosuberic acid [(2S,7S)-2,7-diaminooctanedioic acid, 29, n = 4]. Despite the simplicity of this structure (Scheme 12), the two amino and two carboxy groups must be selectively protected for convenient application in solution and/or solid-phase peptide synthesis. 

Scheme 13 Stereoselective Synthesis of Selectively Protected meso-2,7-Diaminosuberic Acid...

V"-Boc-7Va -Z-L,L-diaminosuberic acid co-tert-butyl ester or bis(7V"-Boc)-L,L-diaminosuberic acid synthesized by the mixed Kolbe electrolytic carboxylative dimerization method was successfully utilized in the synthesis of nonreducible bicyclic analogues of somatostatin1491 or hematoregulatory peptide (pGlu-Glu-Asp)2-Dsu-(Lys)2, respectively.[50]... 

Derivatives of 2,7-diaminosuberic acid and 2,4-diaminoadipic acid by Kolbe reaction L — Biebl et al. (1998)... 

J. Rudinger, K. Jost, A biologically active analogue of oxytocin not containing a disulfide group. Experientia 20 570-571 (1964) O. Keller, J. Rudinger, Synthesis of [l,6-a,a -diaminosuberic acid] oxytocin ( dicarbaoxytocin ). Helv. Chim. Acta 57 1253-1259 (1974) F.H. White Jr., Reduction and reoxidation of disulfide bonds Methods of Enzymology 11 (C.H.W. Hirs Ed.) Academic, New York 1967, pp. 481-484... 

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