Controllable Sulfoxidation and Sulfenylation with Organic Thiosulfate Salts via Dual Electron- and Energy-Transfer Photocatalysis

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.

亚砜（Sulfoxides）与硫醚（sulfides）是有机分子中两类重要的官能团，二者含有不同价态的硫元素。在光催化条件下，通过简便调控反应气氛，可精准调控以常见硫化试剂（sulfurating reagents）参与的亚砜化与硫醚化反应。该两类转化分别涉及串联电子/能量转移与单电子转移过程。针对药物与糖类衍生物的后期亚砜化反应已被证实具有极佳的兼容性。可通过切换反应条件，灵活实现含亚砜/硫醚结构的上市药物的发散式形式合成。克级规模实验进一步验证了该实验方案的实用性。