Cp*CoIII-Catalyzed C-H Alkenylation/Annulation Reactions of Indoles with Alkynes: A DFT Study.

The Cp*CoIII-catalyzed C-H functionalization reaction of indoles with alkynes was examined using M06-level DFT calculations. The C≡C bond in the alkyne was inserted into the Co-C bond of an intermediate alkenyl-Co complex given by the acetate-assisted C-H bond activation step. Then the reaction pathway bifurcated into alkenylation and annulation pathways. In the case where AcOH, which was eliminated by ligand exchange for the alkyne, recoordinated to the Co atom, alkenylation proceeded via proton transfer. On the other hand, the annulation pathway to give pyrroloindolone became significant in the case where the ring-closure C-C bond formation was followed by the attachment of AcOH. At a high temperature (393 K), the difference in the Gibbs free energy between the transition state for proton transfer in the alkenylation pathway and that for the ring-closure C-C bond formation in the annulation pathway was relatively small, so both reactions could proceed. In addition, we also found another pathway to provide the directing-group migration on the way to annulation. This finding well elucidates the recent experimental report that tetrasubstituted alkenes were obtained as the major product under different conditions.