Chemoselective Synthesis of N-Terminal Cysteinyl Thioesters via ß,γ-C,S Thiol-Michael Addition.

Dehydroalanine (ΔAla) is a highly electrophilic residue that can react efficiently with sulfur nucleophiles to furnish cysteinyl analogues. Herein, we report an efficient synthesis of N-terminal cysteinyl thioesters, suitable for S, N-acyl transfer, based on ß,γ-C,S thiol-Michael addition. Both ionic and radical-based methodologies were found to be efficient for this process.