Catalysis with Supramolecular Carbon‐Bonding Interactions

Herein, we describe a new catalysis platform, supramolecular carbon‐bonding catalysis, which exploits the highly directional weak interactions between carbon centers of catalysts and electron donors to drive chemical reactions. To demonstrate this catalysis approach, we discovered a class of cyclopropane derivatives incorporated with carbonyl, ester and cyano groups as catalysts which showed general catalysis capability in different types of benchmark reactions. Among these typical examples, a challenging tail‐to‐head terpene cyclization can be achieved by supramolecular carbon‐bonding catalysis. The co‐crystal structures of catalyst and electron donors, comparison experiments, and titrations support a catalysis mode of carbon‐bonding activation of Lewis basic reactants. Supramolecular carbon‐bonding catalysis was established as a new platform for organic synthesis. A class of versatile catalysts was discovered which showed catalytic capability in different benchmark reactions, thus demonstrating the wide potential of this catalysis strategy.