Kinetically Controlled Chemoselective Cyclization Simplifies the Access to Cyclic and Branched Peptides.

A bis(2-sulfanylethyl)amido group reacts significantly faster with cysteinyl peptides when installed on the C-terminal end of a peptide in comparison with the side-chain of Asp and Glu. This property enabled the design of a kinetically controlled chemoselective peptide cyclization reaction, giving straightforward access to cyclic and branched peptides in one pot.