Non-ribosomal peptides (NRP) are biosynthesized by modular, assembly line-like megasynthetases known as non-ribosomal peptide synthetases (NRPS).  During NRP biosynthesis, precursors and intermediates are covalently tethered to modules within the NRPS assembly line, where the sequence of monomers in the NRP is collinear with respect to the sequence of modules in the associated NRPS.  Recently, we identified several alkene-containing NRP for which the NRPS module responsible for incorporating these monomers are predicted or have been reported to be selective for incorporating the corresponding alkane instead.  We propose that two such natural products utilize a hydroxylation/dehydration sequence to effect desaturation, and have identified the hydroxylases responsible for the first step in this sequence.  We further propose that the subsequent dehydration occurs via an unusual diversion of a reported NRPS-catalyzed epimerization reaction.

Cryptic hydroxylations enabling dehydration in non-ribosomal peptide synthesis

ACS Fall 2021

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