Codinaeopsin


Codinaeopsin is an antimalarial alkaloid isolated from a endophytic mold found in Vochysia trees in Costa Rica. It is reported to have bioactivity against Plasmodium falciparum with an IC50 = 2.3 μg/mL. Pure codinaeopsin was reported to be isolated with a total yield of 18 mg/mL from cultured fungus. The biosynthesis of codinaeopsin involves a polyketide synthase-nonribosomal [peptide synthetase] 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.
[Image:PKS1.png|center|800px|Figure 1. Formation of linear polyketide]

Formation of tetramic acid (2,4-pyrrolidinone)

is introduced by a nonribosomal peptide synthetase module and results in the central heterocyclic tetramic acid. 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.

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.
[Image:NRPS.png|center|800px|Figure 2. Formation of tetramic acid and cyclization of PKS unit]