Biosynthesis of the Red Algal Diterpene Peyssonnosol in Bacteria

Two diterpene synthases (DTSs) for peyssonnosol and peyssonnosol B were discovered in bacteria. Their enzyme mechanisms were investigated through isotopic labelling experiments, density functional theory (DFT) calculations and site-directed mutagenesis, yielding biosynthetically related molecules that gave important insights into the terpene cyclisation cascade. In the present case, several mechanisms in line with the isotopic labelling experiments could be formulated. Only an extended experimental approach in combination with computational chemistry ultimately resulted in a refined mechanistic model.