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dhAAs also undergo enzymatic modification. (A) Enzymes involved in lantibiotic biosynthesis catalyze conjugate additions using S, C, and N nucleophiles. (B) Pyridine synthases from thiopeptide biosynthesis install pyridine rings via a formal aza-[4+2] cycloaddition between two Dhas. LP = leader peptide, B = base. (C) Amino acid ammonium-lyases and aminomutases use a modified dhAA to breakdown amino acids and generate β-amino acids, as in the cancer drug, Taxol.
