The efficient control of the regiochemistry of the Diels− Alder adducts which are formed in excellent yields from 1, 3-dienes and alkynylsilanes can be realized utilizing cobalt complexes with a pyridine-imine ligand or a dppe ligand, respectively. The application of 2- trimethylsilyloxy-1, 3-butadiene leads to a very interesting cyclohexenone derivative suitable for further transformations.