Abstract
Species of the basidiomycete genus Armillaria produce bioactive small molecule natural products, referred to as melleolides. With more than 70 described members, this class of natural products is a prime example for diversity-oriented biosynthesis. Chemically, they represent hybrid molecules, composed of a tricyclic, chiral sesquiterpene protoilludene alcohol, esterified with the tetraketide orsellinic acid or its derivatives. In this review article, we summarize the melleolide’s structural diversity and present—to the extent elucidated—the enzymatic basis how their backbone structures are biosynthesized and modified. We also highlight the current knowledge on their antimicrobial, phytotoxic, and cytotoxic bioactivities, along with a view on the molecular targets of the melleolides, their unparalleled structure-activity relationships, and their modes of action.
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