The 1,2-arylheteroaryl ethane motif stands as a privileged scaffold with promising implications in drug discovery. Conventional de novo syntheses of these molecules have relied heavily on pre-functionalized synthons, entailing harsh conditions and multi-step processes. Here, to address these limitations, we present a modular approach for the direct synthesis of 1,2-arylheteroaryl ethanes using feedstock chemicals, including ethylene, arenes and heteroarenes. We disclosed a photo triplet-energy-transfer-initiated radical cascade process, leveraging homolytic cleavage of C–S bonds in aryl sulfonium salts as the key step to access aryl radicals with excellent regioselectivity. This method allows for rapid structural diversification of bioactive molecules, showcasing excellent functional group tolerance and streamlining the synthesis of bioactive compounds and their derivatives. Furthermore, our approach can be extended to propylene, non-gaseous terminal alkenes and various other electrophilic radical precursors, including heteroaryl radicals, hydroxyl radicals, trifluoromethyl radicals and α-carbonyl alkyl radicals. This study highlights the significance of radical polarity matching in designing selective multi-component couplings.

1,2-芳基杂芳基乙烷基序是一种特殊的支架，在药物发现方面具有广阔的前景。这些分子的传统从头合成在很大程度上依赖于预功能化的合成子，需要苛刻的条件和多步骤的过程。在这里，为了解决这些限制，我们提出了一种使用乙烯、芳烃和杂芳烃等原料化学品直接合成 1,2-芳基杂芳基乙烷的模块化方法。我们公开了一种光三重态能量转移引发的自由基级联过程，利用芳基锍盐中C-S键的均裂作为获得具有优异区域选择性的芳基自由基的关键步骤。该方法可以实现生物活性分子的快速结构多样化，表现出优异的官能团耐受性并简化生物活性化合物及其衍生物的合成。此外，我们的方法可以扩展到丙烯、非气态末端烯烃和各种其他亲电自由基前体，包括杂芳基、羟基、三氟甲基和α-羰基烷基。这项研究强调了激进极性匹配在设计选择性多元件耦合中的重要性。