Photocatalyzed Oxidative Decarboxylation Forming Aminovinylcysteine Containing Peptides

Abstract

The formation of (2S,3S)-S-[(Z)-aminovinyl]-3-methyl-D-cysteine (AviMeCys) substructures was developed based on the photocatalyzed-oxidative decarboxylation of lanthionine-bearing peptides. The decarboxylative selenoetherification of the N-hydroxyphthalimide ester, generated in situ, proceeded under mild conditions at −40 °C in the presence of 1 mol% of eosin Y-Na2 as a photocatalyst and the Hantzsch ester. The following β-elimination of the corresponding N,Se-acetal was operated in a one-pot operation, led to AviMeCys substructures found in natural products in moderate to good yields. The sulfide-bridged motif, and also the carbamate-type protecting groups, such as Cbz, Teoc, Boc and Fmoc groups, were tolerant under the reaction conditions.