Cytochrome P450-Induced Backbone Rearrangements in Terpene Biosynthesis of Plants

Terpenes, the largest class of plant specialized products, are built from C5 building blocks via terpene synthases and oxidized by cytochrome P450 enzymes (CYPs) for structural diversity. In some cases, CYPs do not simply oxidize the terpene backbone, but induce backbone rearrangements, methyl group shifts, and carbon–carbon (C–C) scissions. Some of these reactions were characterized over 25 years ago, but most of them were reported in recent years, indicating a highly dynamic research area. These reactions are involved in mono-, sesqui-, di- and triterpene metabolism and provide key catalytic steps in the biosynthesis of plant hormones, volatiles, and defense compounds. Many commercially relevant terpenoids require such reaction steps in their biosynthesis such as triptonide (rodent pest management), secoiridoids (flavor determinants), as well as ginkgolides, cardenolides, and sesquiterpene lactones with pharmaceutical potential. Here, we provide a comprehensive overview of the underlying mechanisms.