Photocatalytic Copper-Mediated Functionalization of Aryl Iodides with Fluoride and Water

Copper-mediated functionalization of aryl halides with fluoride or water offers an attractive approach for isotope incorporation, as F-18 and O-18 are readily available in the form of [18F]-fluoride or [18O]-water. However, traditional reactions with these nucleophiles often require harsh conditions due to the high activation barrier associated with oxidative addition. Copper-mediated cross-coupling via a radical pathway provides an efficient way to lower the oxidative addition barrier, but formation of C–F and C–O bonds remains challenging, primarily due to the difficulty in achieving compatibility between the electron donor for radical initiation and radical acceptors, such as copper(II) fluoride. Herein, we have developed a highly compatible radical initiation system that enables a visible-light-induced, copper-mediated fluorination or hydroxylation reaction of aryl iodide with fluoride or water. The reaction features mild reaction conditions and high functional group tolerance.