Codinaeopsin Explained

Codinaeopsin is an antimalarial isolated from a fungal isolate found in white yemeri trees (Vochysia guatemalensis) in Costa Rica. It is reported to have bioactivity against Plasmodium falciparum with an IC50 = 2.3 μg/mL (4.7 μM). Pure codinaeopsin was reported to be isolated with a total yield of 18 mg/mL from cultured fungus.[1] The biosynthesis of codinaeopsin involves a polyketide synthase-nonribosomal peptide synthetase (PKS-NRPS) hybrid.

Biosynthesis

Formation of linear polyketide

The first step of the biosynthesis of codinaeopsin involves the assembly of the a linear polyketide by use of seven modules and incorporation of six methylmalonyl CoAs and one malonyl CoA by polyketide synthases (type I PKSs).[1]

Formation of tetramic acid (2,4-pyrrolidinone)

L-Tryptophan is introduced by a nonribosomal peptide synthetase (NRPS) module and results in the central heterocyclic tetramic acid (2,4-pyrrolidinone). The formal oxidation-reduction is found to be achieved by a series of tautomeric shifts involving enol and imine intermediates in the ring and consistent by discovery both C-2’ epimers.[1]

Cyclization of PKS-assembled unit

The PKS unit is hypothesized to cyclize by a Diels-Alder-like addition similar to other natural products such as lovastatin and solanapyrone.[2]

Notes and References

  1. Kontnik. Renee. 2008. Codinaeopsin, an Antimalarial Fungal Polyketide. Org. Lett.. 10. 18. 4149–4151. 10.1021/ol801726k. Clardy, Jon. 18698786. Jon Clardy. 2626159.
  2. Auclair. Karine. Karine Auclair. Sutherland. Andrew. Kennedy. Jonathan. Witter. David J.. Van den Heever. Johan P.. Hutchinson. C. Richard. Vederas. John C.. Lovastatin Nonaketide Synthase Catalyzes an Intramolecular Diels−Alder Reaction of a Substrate Analogue. Journal of the American Chemical Society. 122. 46. 2000. 11519–11520. 0002-7863. 10.1021/ja003216+.