Exploring the Chemical Space Accessed by Chiral Pool Terpenes. The (-)-Caryophyllene Oxide Paradigm.

Terpenes represent a flourishing source of structural motifs that can be converted into several more complex architectures. Realization of such transformations in a concise and efficient manner adds great value to the starting material. Herein, we study the case of (-)-caryophyllene oxide and convert it into natural sesquiterpenoids (rumphellolide K, rumphellaone A, and antipacid A), thus expanding the chemical space accessed by its privilege structure. Our semisyntheses are short and rely on reagent-dictated stereo- and chemoselectivity.