Radical-polar crossover (RPC) chemistry is an emerging field characterized by transformations that involve the coexistence of both radical and ionic species. Since the reactivities of radical and ionic intermediates are orthogonal, applying these two mechanisms in sequence provides significant advantages in the construction of complex molecular architectures. The concept of the RPC approach has become increasingly important in the total synthesis of natural products. This Synopsis presents several examples to showcase recent advancements in this area, including our research on the synthesis of Ganoderma meroterpenoids. In these selected cases, RPC reactions enhance the building of structural complexity and improve overall synthetic efficiency that cannot be achieved by standard synthetic methods.

Department of Organic Chemistry and Center for Molecular Biosciences University of Innsbruck 6020 Innsbruck Austria

Department of Organic Chemistry Palacký University Olomouc 77900 Olomouc Czech Republic

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