Currently, the selective activation of C(sp³)–F bonds and C–C bonds constitute one of the most widely used procedures for the synthesis of high-value products that range from pharmaceuticals to agrochemical applications. While numerous examples of these two methods have been reported in their respective fields, the processes which merge the activation of both single C(sp³)-F bonds and C–C bonds in one step still remain elusive. Here, we demonstrate the controllable defluoroalkylation–distal functionalization of trifluoromethylarenes with unactivated alkenes via distal heteroaryl migration. This is proposed to proceed via tandem C(sp³)–F and C–C bond cleavage using visible-light photoredox catalysis combined with Lewis acid activation. This strategy provides facile and flexible access to multiply functionalized α,α-difluorobenzylic ketones in useful yields (up to 88%) under mild conditions. The products can be further transformed into other valuable compounds, demonstrating the method’s utility.

^{目前，C(sp 3} )–F 键和 C–C 键的选择性激活构成了从药物到农化应用等高价值产品合成中使用最广泛的程序之一。虽然这两种方法在各自的领域中已经有大量的例子被报道，但将单个 C(sp ³ )-F 键和 C-C 键的激活合并到一个步骤中的过程仍然难以捉摸。在这里，我们通过远端杂芳基迁移展示了三氟甲基芳烃与未活化烯烃的可控脱氟烷基化远端功能化。建议通过串联 C(sp ³)-F 和 C-C 键裂解使用可见光光氧化还原催化结合路易斯酸活化。该策略提供了在温和条件下以有用的产率（高达 88%）轻松灵活地获得多官能化α、α-二氟苄酮。产品可以进一步转化为其他有价值的化合物，证明了该方法的实用性。