Sulfoxides
and sulfides are two important functional groups in
organic molecules, containing different valence states of sulfur.
Both sulfoxidation and sulfenylation with common sulfurating reagents
were successfully tuned via a facile variation of the atmosphere under
photocatalyzed conditions. The sulfoxidation and sulfenylation transformations
involved tandem electron-/energy-transfer and single-electron-transfer
processes, respectively. Late-stage sulfoxidation for pharmaceuticals
and sugar derivatives was established to be highly compatible. Divergent
formal syntheses of sulfoxide/sulfide-containing marketed pharmaceuticals
were switchably implemented. Gram-scale operations further demonstrated
the practicability of the protocol.