Modes of inactivation of trichodiene synthase by a cyclopropane-containing farnesyldiphosphate analog.

We describe quantum chemical calculations on the rearrangement of carbocations derived from a cyclopropane-containing analog of farnesyl diphosphate (FPP). These calculations reveal significant differences between the energetics for rearrangement of this analog and FPP itself, suggesting that the behavior of this substrate analog likely does not mirror that of the natural substrate. In addition, our results point to new mechanisms by which this FPP analog inactivates trichodiene synthase.