Total synthesis of angelone enabled by a remarkable biomimetic sequence

The natural product angelone was readily accessed with a remarkable biomimetic journey that sequentially features carbonyl formation–elimination, 6π-electrocyclization, visible light-promoted singlet O2 Diels–Alder reaction, Kornblum–DeLaMare-type peroxide rearrangement, 6π-electrocyclic ring-opening, and conjugative addition–elimination as the key steps. With key intermediates isolated and characterized, this study stands to reveal a rare system in which bio-inspired synthetic strategies were found to mirror experimental realities. [Display omitted]