Shanghai Key Laboratory of Green Chemistry and Chemical Process, Department of Chemistry, East China Normal University, 3663 North Zhongshan Rd., Shanghai, 200062, P. R. China.
National Center for Drug Screening, Laboratory of Drug Research Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai, 201203, P. R. China.
Angew Chem Int Ed Engl. 2019 Sep 16;58(38):13499-13506. doi: 10.1002/anie.201906080. Epub 2019 Aug 8.
Oxygenation is a fundamental transformation in synthesis. Herein, we describe the selective late-stage oxygenation of sulfur-containing complex molecules with ground-state oxygen under ambient conditions. The high oxidation potential of the active uranyl cation (UO ) enabled the efficient synthesis of sulfones. The ligand-to-metal charge transfer process (LMCT) from O 2p to U 5f within the O=U=O group, which generates a U center and an oxygen radical, is assumed to be affected by the solvent and additives, and can be tuned to promote selective sulfoxidation. This tunable strategy enabled the batch synthesis of 32 pharmaceuticals and analogues by late-stage oxygenation in an atom- and step-efficient manner.
氧合作用是合成中的一种基本转化。在此，我们描述了在环境条件下用基态氧选择性地对含硫复杂分子进行晚期氧合。活性铀阳离子（UO ）的高氧化电位使亚砜的高效合成成为可能。O=U=O 基团内 O 2p 到 U 5f 的配体到金属电荷转移过程（LMCT），生成 U 中心和氧自由基，据推测受溶剂和添加剂影响，可以进行调节以促进选择性氧化。这种可调策略以原子经济性和步骤经济性的方式通过晚期氧合批量合成了 32 种药物和类似物。
