Overlooked families and poorly studied classes of natural products frequently harbor genes that encode proteins that catalyze cryptic or unpredictable transformations. Studying these transformations can provide valuable insights into the biosynthesis of an entire family or class of natural products. These insights pave the way towards establishing universal biosynthetic principles for a natural product class or family and are a first step towards the design of novel, non-natural biosynthetic pathways.
Moreover, we use retrobiosynthetic analysis to identify the biosynthetic gene clusters for characterized natural products that are likely produced by non-canonical biosynthetic pathways harboring unusual biosynthetic enzymes or likely arising from spontaneous reactions.
Unusual proteins might be employed in chemoenzymatic syntheses to obtain difficult-to-synthesize chemical products and insights into the spontaneous formation of complex natural products might inspire biomimetic syntheses of these compounds.