Formation of a C-C double bond from two aliphatic carbons. Multiple C-H activations in an iridium pincer complex.

The search for novel, atom-economic methods for the formation of C-C bonds is of crucial importance in synthetic chemistry. Especially attractive are reactions where C-C bonds are formed through C-H activation, but the coupling of unactivated, alkane-type C -H bonds remains an unsolved challenge. Here, we report iridium-mediated intramolecular coupling reactions involving up to four unactivated C -H bonds to give carbon-carbon double bonds under the extrusion of dihydrogen. The reaction described herein is completely reversible and the direction can be controlled by altering the reaction conditions. With a hydrogen acceptor present a C-C double bond is formed, while reacting under dihydrogen pressure leads to the reverse process, with some of the steps representing net C -C bond cleavage. Mechanistic investigations revealed a conceptually-novel overall reactivity pattern where insertion or deinsertion of an Ir carbene moiety, formed double C-H activation, into an Ir-C bond is responsible for the key C-C bond formation and cleavage steps.