Use of the Wolff Rearrangement of Diazo Ketones from Amino Acids as a synthetic method for the formation of oligonucleo-peptides: A novel approach to chimeric biomolecules

✍ Scribed by Christel Guibourdenche; Dieter Seebach; François Natt

• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: German
• Weight: 696 KB
• Volume: 80
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.19970800102

✦ Synopsis

Abstract

Photolysis and Ag‐benzoate‐catalyzed decomposition of the diazo ketones 2 and 4 derived from Z‐Ala‐OH and Z‐Ala‐Ala‐OH in the presence of oligonucleotide derivatives bearing at the 5′‐terminus an NH~2~ instead of the OH group, or an aminohexyl phosphate group lead to Z‐protected 3‐aminobutanoyl and to Z‐Ala‐β‐HAla derivatives, respectively (conjugates 12, 13, and 17‐23, Schemes 3‐5), In solution, this amide‐forming acylation reaction could be realized only with oligomers containing up to 8 unprotected nucleotide building blocks (Schemes 3 and 4). With the analogous polymer‐bound and protected oligonucleotide derivatives as amino nucleophiles, excellent yields were obtained with all chain lengths tested (up to 15mer Scheme 5), The products were purified by reversed‐phase HPLC and characterized by MALDI‐TOF mass spectrometry (Figs. 2–4, Table 2) and by capillary gel electrophoresis (Fig.2).