Distinct hydrogen atom transfer and radical capture reactivity of copper( <scp>iii</scp> ) OH/F complexes enables site-selective C(sp ³ )–H ¹⁸ F-fluorination

High-valent metal intermediates play a key role in C(sp³)-H functionalization reactions in both enzymatic catalysis and organometallic chemistry. Despite its generality, this strategy often requires a single metal complex to efficiently mediate both hydrogen atom transfer and radical capture-a combination challenging to achieve. To overcome this limitation, we propose a decoupled approach, where separate high-valent metal complexes independently perform hydrogen atom transfer (HAT) and radical capture (RC). As a proof of concept, we leveraged the complementary reactivity of copper(iii) hydroxide (efficient for HAT) and copper(iii) fluoride (efficient for RC) to develop a decoupled ¹⁸F-fluorination protocol. The distinct reactivity of copper(iii) hydroxide and copper(iii) fluoride not only enables precise control over the C-H activation process but also preserves the valuable [¹⁸F]fluoride for radical capture, preventing its consumption during HAT. With this mechanistic insight, we achieved the selective fluorination of α-ethereal, benzylic, and allylic C-H bonds, facilitating the synthesis of a series of ¹⁸F-labeled organic molecules.