Aryl–aryl cross-coupling constitutes one of the most widely used procedures for the synthesis of high-value materials that range from pharmaceuticals to organic electronics and conducting polymers. The assembly of (hetero)biaryl scaffolds generally requires multiple steps; coupling partners must be functionalized before the key bond-forming event is considered. The development of selective C–H arylation processes in arenes—which sidestep the need for prefunctionalized partners—is thus crucial for streamlining the construction of these key architectures. Here we report an expedient, one-pot assembly of (hetero)biaryl motifs using photocatalysis and two non-prefunctionalized arene partners. The approach is underpinned by the functionalization of a C–H bond in an arene coupling partner using the interrupted Pummerer reaction. A unique pairing of the organic photoredox catalyst and the intermediate dibenzothiophenium salts enables highly selective reduction in the presence of sensitive functionalities. The utility of the metal-free, one-pot strategy is exemplified by the synthesis of a bioactive natural product and the modification of complex molecules of societal importance.

芳基-芳基交叉偶联是用于合成高价值材料（从药物到有机电子产品和导电聚合物）的最广泛程序之一。（杂）联芳基支架的组装通常需要多个步骤。在考虑形成关键键的事件之前，必须对耦合伙伴进行功能化。因此，在竞技场中开发选择性的C–H芳基化过程（避开对预先功能化的合作伙伴的需求）对于简化这些关键体系结构的构建至关重要。在这里，我们报告使用光催化和两个未预官能化的芳烃伙伴的方便，一锅（杂）联芳基图案的大会。该方法的基础是使用间断的Pummerer反应在芳烃偶联伙伴中将C–H键官能化。有机光氧化还原催化剂和中间体二苯并噻​​吩鎓盐的独特配对能够在敏感官能团存在的情况下高度选择性地还原。无金属一锅法的效用以生物活性天然产物的合成和具有社会重要性的复杂分子的修饰为例。