Generation of Dithianyl and Dioxolanyl Radicals Using Photoredox Catalysis: Application in the Total Synthesis of the Danshenspiroketallactones via Radical Relay Chemistry.
Yifan DengMinh D NguyenYike ZouKendall N HoukAmos B Smith IiiPublished in: Organic letters (2019)
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.