Synthesis of Sulfur-Containing Oxindoles by Photoinduced Alkene Difunctionalization via Sulfur 1,2-Relocation.

Organosulfur compounds are prevalent in various natural products, which have been widely applied in agrochemicals and pharmaceuticals. Herein, a new approach for the efficient construction of sulfur-containing oxindoles by photoinduced alkene difunctionalization via sulfur 1,2-relocation is developed. The method exhibited a high functional group tolerance and broad substrate compatibility. A library of sulfur-containing oxindole derivatives were synthesized under mild conditions (metal-, photocatalyst-, and additive-free). Mechanistic investigations revealed this photochemical process was triggered by the formation of an EDA complex of oxindole enolates with a redox-active ester, and the in situ generation of alkenes from the C-S bond cleavage of β-sulfanyl radicals was a key step in this transformation.