Bifunctional Sesquiterpene/Diterpene Synthase Agr2 from Gives Rise to the Novel Diterpene Cyclocybene.

is a model mushroom belonging to the fungal phylum Basidiomycota. Among others, is known for its diverse terpenome, containing various volatile and nonvolatile terpenes and terpenoids. Here, we deepen the knowledge on their biosynthetic pathways by studying the terpene synthase Agr2 in detail. In contrast to previous studies, the heterologous production of Agr2 in the agaric host revealed the production of two terpenes, one of which was the already known sesquiterpene viridiflorene. The other one was a so far unknown diterpene that had to be isolated and purified by means of preparative RP-HPLC for structure elucidation. 1D- and 2D-NMR experiments revealed the compound as the novel diterpene cyclocybene, pointing to the bifunctionality of Agr2 to produce both a sesquiterpene and a diterpene.