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Chemical synthesis of proteins may provide proteins(e.g.,post-translationally modified proteins,photocaged proteins,mirror-image proteins)that are difficult to obtain via recombinant technology.The most successful strategy for protein chemical synthesis is native chemical ligation(NCL).This method relies on the use of peptide thioesters as key intermediates,which are often difficult to prepare through Fmoc solid-phase peptide synthesis(SPPS).We recently developed peptide hydrazides as an efficient thioester equivalent for protein chemical synthesis[1].The utility of peptide hydrazides is shown for the total synthesis of post-translationally modified histones,photocaged protein probes,transmembrane proteins and mirror-image proteins.