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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
Author(s) -
Guibourdenche Christel,
Seebach Dieter,
Natt François
Publication year - 1997
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19970800102
Subject(s) - chemistry , acylation , diazo , oligonucleotide , amide , protecting group , amino acid , stereochemistry , capillary electrophoresis , combinatorial chemistry , organic chemistry , chromatography , catalysis , dna , biochemistry , alkyl
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 ).