Generation of Thiyl Radicals from Air-Stable, Odorless Thiophenol Surrogates: Application to Visible-Light-Promoted C-S Cross-Coupling
Generation of Thiyl Radicals from Air-Stable, Odorless Thiophenol Surrogates: Application to Visible-Light-Promoted C-S Cross-Coupling
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从空气稳定、无味的苯硫酚替代物生成硫基自由基：在可见光促进的 C-S 交叉偶联中的应用
DOI：
10.1055/s-0041-1737816
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Ball L
中科院分区：
文献类型：
--
作者：
Ball L
苯硫酚的合成多功能性被其空气敏感性和恶臭所抵消。事实证明，S-芳基异硫脲盐可用作硫基自由基的前体，将这些空气稳定、无味盐的实际益处从离子型扩展到单电子型。异硫脲盐是通过（杂）芳基碘化物和硫脲的镍催化交叉偶联获得的，并在阴离子交换后以自由流动的固体形式分离出来。明智地选择氧化还原无害的抗衡阴离子可以在自由基过程中使用这些方便的苯硫酚替代物，例如通过光促进的S-芳基化合成非对称二芳基硫醚。
The synthetic versatility of thiophenols is offset by their air-sensitivity and foul odor. It is demonstrated thatS-aryl isothiouronium salts can be used as precursors to thiyl radicals, extending the practical benefits of these air-stable, odorless salts from ionic to single electron manifolds. The isothiouronium salts are accessed via Ni-catalyzed cross-coupling of (hetero)aryl iodides and thiourea and are isolated as free-flowing solids following anion exchange. Judicious choice of a redox-innocent counteranion enables use of these convenient thiophenol surrogates in radical processes, as is exemplified by the synthesis of non-symmetrical diaryl thioethers via light-promotedS-arylation.