Iridium(I)‐Catalyzed Intramolecular Hydrocarbonation of Alkenes: Efficient Access to Cyclic Systems Bearing Quaternary Stereocenters

A catalytic, versatile and atom‐economical C−H functionalization process that provides a wide variety of cyclic systems featuring methyl‐substituted quaternary stereocenters is described. The method relies on the use of a cationic Ir^I–bisphosphine catalyst, which promotes a carboxamide‐assisted activation of an olefinic C(sp²)−H bond followed by exo‐cyclization to a tethered 1,1‐disubstituted alkene. The extension of the method to aromatic and heteroaromatic C−H bonds, as well as developments on an enantioselective variant, are also described.