Enzymatic Synthesis of Demethylated Sesquiterpenes From 14‐ nor ‐Farnesyl Pyrophosphate

Previous work has revealed that terpene synthases can efficiently convert non‐natural substrate analogs, which often leads to interesting new structures. In the present study 10 sesquiterpene synthases were used to convert 14‐ nor ‐FPP into demethyl (C 14 ) sesquiterpenes. The obtained products were isolated and their structures elucidated through NMR spectroscopy. In most cases the demethyl analogs corresponding to the natural products formed from farnesyl pyrophosphate were obtained, but sometimes the structural change in the substrate resulted in a change of reactivity and consequently the formation of structurally deviating products. The absolute configurations were assigned based on biosynthetic considerations and on a comparison of optical rotations to those of the natural C 15 analogs.