Gold(I)-Catalyzed Intramolecular C(sp3)−H Insertion by Decarbenation of Cycloheptatrienes

A novel synthesis of indanes and dihydronaphtalenes based on the intramolecular insertion into C(sp3)−H bonds of gold(I) carbenes generated by retro‐Buchner reaction (decarbenation) has been developed. Deuterium‐labeling and kinetic isotope effect experiments, DFT calculations, and generation of the proposed carbene intermediate from a well‐characterized gold(I) carbenoid support the involvement of a three‐center concerted mechanism for the C(sp3)−H functionalization process.