Generation of Dithianyl and Dioxolanyl Radicals Using Photoredox Catalysis: Application in the Total Synthesis of the Danshenspiroketallactones via Radical Relay Chemistry

Visible-light-induced generation of dithianyl and dioxolanyl radicals via selective hydrogen atom transfer (HAT) has been achieved. This radical relay tactic enables remote C(sp3)–H functionalization to permit rapid access to polyol and spiroketal segments, and in turn has been exploited as a key synthetic construct in the total synthesis of the danshenspiroketallactones. The conformational stability of the danshenspiroketallactones has also been defined via experiments and DFT calculations.