Granados Albert, Cabrera-Afonso María Jesús, Escolano Marcos, Badir Shorouk O, Molander Gary A
Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, PA 19104-6323, United States.
These authors contributed equally.
Chem Catal. 2022 Apr 21;2(4):898-907. doi: 10.1016/j.checat.2022.03.007. Epub 2022 Apr 5.
Sulfone-containing compounds are prevalent building blocks in pharmaceuticals and other biomolecules, and they serve as key intermediates in the synthesis of complex scaffolds. During the past decade, several methods have been developed to access sulfones. These strategies, however, require the use of strong reaction conditions, limiting their substrate scope. Recently, visible light-mediated transformations have emerged as novel platforms to access unprecedented structural motifs. This report demonstrates a thianthrenium-enabled sulfonylation via intra-complex charge transfer to generate transient aryl- and persistent sulfonyl radicals that undergo selective coupling to generate alkyl- and (hetero)aryl sulfones under ambient conditions. Importantly, this strategy allows retention of halide handles, presenting a complementary approach to transition metal-mediated photoredox couplings. Furthermore, this sulfonylation allows high functional group tolerance and is amenable to late-stage functionalization of complex biomolecules. Mechanistic investigations support the intermediacy of electron donor-acceptor (EDA) complexes.
含砜化合物是药物和其他生物分子中普遍存在的结构单元，并且它们在复杂骨架的合成中充当关键中间体。在过去十年中，已经开发了几种制备砜的方法。然而，这些策略需要使用强烈的反应条件，限制了它们的底物范围。最近，可见光介导的转化已成为获得前所未有的结构基序的新型平台。本报告展示了一种通过配合物内电荷转移实现的噻蒽鎓介导的磺酰化反应，以生成瞬态芳基和持久性磺酰基自由基，这些自由基在环境条件下进行选择性偶联以生成烷基和（杂）芳基砜。重要的是，该策略允许保留卤化物官能团，为过渡金属介导的光氧化还原偶联提供了一种互补方法。此外，这种磺酰化反应具有高官能团耐受性，适用于复杂生物分子的后期官能团化。机理研究支持电子供体 - 受体（EDA）配合物的中间体性质。
