Abstract This Concept highlights the discovery and development of oxidative coupling reactions catalyzed by the hypoiodite (IO − ) or iodite (OIO − ) ion, which are generated in situ from iodide (I − ) ion with hydrogen peroxide or tert ‐butyl hydroperoxide as an environmentally benign oxidant. The most important features of these catalytic systems are 1) metal‐free oxidation, 2) milder reaction conditions, 3) high chemoselectivity (they tolerate a wide range of various functional groups), 4) operational simplicity, and 5) water or tert ‐butyl alcohol as the only byproduct derived from the co‐oxidant used.

Catalysis with In Situ‐Generated (Hypo)iodite Ions for Oxidative Coupling Reactions