Ribosomal Synthesis of Backbone-Macrocyclic Peptides Containing γ-Amino Acids

Mine's in the middle: We report here a novel methodology for the ribosomal synthesis of backbone‐macrocyclic peptides containing γ‐amino acids under the reprogrammed genetic code. Integration of reprogrammed initiation by using exotic dipeptides with C‐terminal diketopiperadine‐thioester formation has successfully afforded backbone‐cyclized peptides with γ‐amino acids at an internal position.