Cytochrome P450 _Blt Enables Versatile Peptide Cyclisation to Generate Histidine‐ and Tyrosine‐Containing Crosslinked Tripeptide Building Blocks

Abstract We report our investigation of the utility peptide crosslinking cytochrome P450 enzymes from biarylitide biosynthesis to generate a range cyclic tripeptides simple synthons. The crosslinked produced by this include both tyrosine‐histidine (A− N −B) and tyrosine‐tryptophan O tripeptides, latter rare example phenolic crosslink an indole moiety. Tripeptides are easily isolated following proteolytic removal leader can incorporate wide amino acids in residue inside tripeptide. Given crosslinks important natural products synthetic challenge that these represent, have potential play roles as tools generation high‐value for incorporation synthesis, which be yet further diversified using selective chemical techniques through specific handles contained within tripeptides.