Revealing coupling patterns in isoprenoid alkylation biocatalysis.

Diversity of scaffold structure and function is a hallmark of the >50,000 isoprenoid natural products such as taxol. Whereas most members of this class are assembled by iterative head-to-tail enzymatic joining reactions between delta2- and delta3-isopentenyl diphosphate (IPP) monomers, dimerization of two delta2-IPP molecules has now been shown to account for three additional modes of "irregular" coupling patterns at the level of C10 monoterpene scaffolds.