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Keywords:

  • alkaloids;
  • biosynthesis;
  • electron transfer;
  • metabiosynthesis;
  • natural products
Thumbnail image of graphical abstract

Game-SET-match: Pyrrole aminoimidazole alkaloids (PAIs) are metabiosynthesized from chlorinated analogues of oroidin by cell-free enzyme preparations from PAI-producing sponges. Evidence and implications for the biosynthesis of PAIs include putative single-electron transfers (SETs) that promote C[BOND]C bond-forming reactions of precursors.