Shaping the Polypropionate Biosynthesis in the Solar‐Powered Mollusc Elysia viridis

Polypropionates that incorporate pyrones are a family of polyketides featuring the chemistry of a few marine molluscs capable of phototrophic CO 2 fixation as a result of storing viable symbiotic chloroplasts in their bodies. The role and origin of these molecules is poorly investigated, although the unusual biological activities and chemistry of these natural products have recently received renewed interest. Here, we report the results of in vivo studies on production of γ‐pyrone‐containing polypropionates in the Mediterranean mollusc Elysia viridis . Biosynthesis of the metabolites in the sacoglossan is shown to proceed through condensation of eight intact C 3 units by polyketide synthase assembly. LC–MS and NMR spectroscopic studies demonstrate that the process involves a pyrone tetraene ( 10 ) as key intermediate, whereas the levels of the final polypropionates ( 6 , 7 and 9 ) are related to each other and show a significant dependence upon light conditions.