Biogenetic space-guided synthesis of rearranged terpenoids

Natural product chemistry is constantly challenged by newly discovered, complex molecules. Elements of complexity arise from unprecedented frameworks, with a large amount of densely packed stereogenic centres and different functional groups along with a generally high oxidation state. As a prime example, rearranged triterpenoids possess all these elements. For their total synthesis, a limit of what is considered sensible in terms of steps and yield is frequently reached. As an alternative, semisynthetic approaches have gained a great amount of attention in recent years. In this featured article, we present our and others' contributions towards the development of efficient and economic syntheses of complex terpenoid natural products and elaborate on the underlying rationale of biogenetic space-guided synthetic analysis.

Automated summary

Natural product chemistry faces constant challenges from newly discovered, complex molecules. These complexities include unprecedented frameworks, densely packed stereogenic centres, different functional groups, and high oxidation states. Rearranged triterpenoids exemplify these complexities. Total synthesis of these compounds often reaches the limits of feasibility in terms of steps and yield, leading to the exploration of semisynthetic approaches. This featured article discusses efficient and economic syntheses of complex terpenoid natural products and delves into the underlying rationale of biogenetic space-guided synthetic analysis.