Solventless Oxidative Coupling of Amines to Imines by Using Transition‐Metal‐Free Metal–Organic Frameworks

Abstract A highly efficient, simple, and versatile transition‐metal‐free metal–organic framework catalytic system is proposed for the oxidative coupling of amines to imines. The catalytic protocol features high activities and selectivities to target products; compatibility with a variety of substrates, including aliphatic amines and secondary amines; and the possibility to efficiently and selectively promote amine cross‐coupling reactions. A high stability and recyclability of the catalyst is also observed under the investigated conditions. Insights into the reaction mechanism indicate the formation of a superoxide species able to efficiently promote oxidative couplings.