The C–S bond is one of the most fundamental chemical bonds in synthetic chemistry. However, how to control the highly reactive thiyl radical and develop new strategies for forming C–S bonds remains a challenging yet elusive objective. Herein, we demonstrate that a triple radical catalytic cycle, specifically the combination of organic photocatalysis, hydrogen atom transfer (HAT) catalysis and a programmed radical relay cycle, can be leveraged to enable the [3 + 2] radical sulfuration of alkenes by carrying out multi-component radical cross-coupling. CS₂ is a masked 1,3-disulfur radical equivalent, successfully leading to five-membered-ring sulfur-containing scaffolds with six C–S bonds. This visible-light-mediated organic photocatalytic mechanism can allow multiple reactive radicals to be used programmatically. Applying this strategy enables us to find new methods for forming chemical bonds that had previously been inaccessible or uninvestigated.

中文翻译：

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有机光催化[3+2]烯烃自由基硫化

C-S键是合成化学中最基本的化学键之一。然而，如何控制高反应性的硫基自由基并开发形成C-S键的新策略仍然是一个具有挑战性且难以实现的目标。在此，我们证明了三自由基催化循环，特别是有机光催化、氢原子转移（HAT）催化和程序化自由基中继循环的组合，可以通过进行以下步骤来实现烯烃的[3 + 2]自由基硫化：多组分自由基交叉偶联。 CS ₂是一种掩蔽的 1,3-二硫自由基等价物，成功地产生了具有六个 C-S 键的五元环含硫支架。这种可见光介导的有机光催化机制可以允许以编程方式使用多个反应性自由基。应用这一策略使我们能够找到形成以前无法实现或未研究的化学键的新方法。