Electron-deficient alkynes as cleavable reagents for the modification of cysteine-containlng peptides in aqueous medium

An efficient method has been developed for the chemoselective cysteine modification of unprotected peptides and proteins in aqueous media through the formation of a vinyl sulfide linkage by using electron-deficient alkynes, including alkynoic amides, esters and alkynones. The terminal alkynone-modified peptides could be converted back into the unmodified peptides (81 % isolated yield) by adding thiols under mild conditions. The usefulness of this thiol-assisted cleavage of the vinyl sulfide linkage in peptides has been exemplified by the enrichment of a cysteine-containing peptide (71% recovery) from a mixture of cysteine-containing and non-cysteine-containing peptides. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.link_to_subscribed_fulltex