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Mechanistic studies of amide bond scission during acidolytic deprotection of Pip containing peptide
Author(s) -
Rubini Chiara,
Osler Alessio,
Calderan Andrea,
Guiotto Andrea,
Ruzza Paolo
Publication year - 2008
Publication title -
journal of peptide science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 66
eISSN - 1099-1387
pISSN - 1075-2617
DOI - 10.1002/psc.1032
Subject(s) - peptide bond , chemistry , bond cleavage , amide , hydrolysis , cleavage (geology) , peptide , pipecolic acid , stereochemistry , amino acid , combinatorial chemistry , medicinal chemistry , catalysis , organic chemistry , biochemistry , geotechnical engineering , fracture (geology) , engineering
Unusual TFA catalyzed cleavage reaction is reported for peptide containing pipecolic acid residues. Although the use of TFA under standard cleavage conditions is sufficiently mild to prevent degradation of the desired products, the amide bond between consecutive pipecolic acid residues is unexpectedly hydrolyzed by standard TFA treatment. The hydrolysis is proposed to proceed via an oxazolinium ion intermediate. This mechanism is supported by H/D exchange as observed by ESI‐MS and NMR experiments. Copyright © 2008 European Peptide Society and John Wiley & Sons, Ltd.