Multi-site functionalization of molecules provides a potent approach to accessing intricate compounds. However, simultaneous functionalization of the reactive site and the inert remote C(sp³)–H poses a formidable challenge, as chemical reactions conventionally occur at the most active site. In addition, achieving precise control over site selectivity for remote C(sp³)–H activation presents an additional hurdle. Here we report an alternative modular method for alkene difunctionalization, encompassing radical-triggered translocation of functional groups and remote C(sp³)–H desaturation via photo/cobalt dual catalysis. By systematically combining radical addition, functional group migration and cobalt-promoted hydrogen atom transfer, we successfully effectuate the translocation of the carbon–carbon double bond and another functional group with precise site selectivity and remarkable E/Z selectivity. This redox-neutral approach shows good compatibility with diverse fluoroalkyl and sulfonyl radical precursors, enabling the migration of benzoyloxy, acetoxy, formyl, cyano and heteroaryl groups. This protocol offers a resolution for the simultaneous transformation of manifold sites.

分子的多位点官能团化提供了一种获得复杂化合物的有效方法。然而，反应位点和惰性远程 C（sp³）-H 的同时功能化带来了艰巨的挑战，因为化学反应通常发生在最活跃的位点。此外，实现对远程 C（sp³）-H 激活的位点选择性的精确控制还存在另一个障碍。在这里，我们报道了一种烯烃二官能化的替代模块化方法，包括自由基触发的官能团易位和通过光/钴双催化的远程 C（sp³）-H 去饱和。通过系统地结合自由基加成、官能团迁移和钴促进的氢原子转移，我们成功地实现了碳-碳双键和另一个官能团的易位，具有精确的位点选择性和显著的 E/Z 选择性。这种氧化还原中性方法与不同的氟烷基和磺酰自由基前体具有良好的相容性，能够迁移苯甲酰氧基、乙酰氧基、甲酰基、氰基和杂芳基。该协议为多流位点的同时转化提供了解决方案。