Structure revision of meroterpenoid natural products enabled by biomimetic total synthesis

Meroterpenoids constitute a vast and structurally diverse family of natural products with mixed biosynthetic origins, found across nearly all forms of life on Earth. Despite their often intricate architectures, meroterpenoid biosynthesis follows a remarkably consistent and predictable chemical logic, driven largely by interactions between electron-rich aromatic rings and terpene-derived building blocks. However, the structural elucidation of these stereochemically complex molecules remains challenging, and misassignments are common. This review highlights the pivotal role of biomimetic total synthesis in enabling the structural reassignment of meroterpenoids, whilst also rationalising their biosynthetic origin, inspiring the design of novel cascade reactions, and even guiding the prediction and discovery of previously unknown natural products.