The Stannum-Ene Reactions of Benzyne and Cyclohexyne with Superb Chemoselectivity for Cyclohexyne.

The stannum-ene reactions of both benzyne and cyclohexyne were realized, which is particularly suitable for cyclohexyne with a broad substrate scope and excellent chemoselectivity. Our DFT calculations via distortion/interaction analysis revealed that both stannum- and hydrogen-ene reactions with cyclohexyne have later transition states due to their higher distortion energies in the transition states than those in benzyne reactions, which lead to enhanced Pauli repulsion as the decisive factor in the interaction energy accompanied with enlarged energy gap between two types of ene reactions. Therefore, excellent chemoselectivity was disclosed in the cyclohexyne-ene reaction.