Catalytic Difunctionalization of Unactivated Alkenes with Unreactive Hexamethyldisilane through Regeneration of Silylium Ions

A metal‐free, intermolecular syn‐addition of hexamethyldisilane across simple alkenes is reported. The catalytic cycle is initiated and propagated by the transfer of a methyl group from the disilane to a silylium‐ion‐like intermediate, corresponding to the (re)generation of the silylium‐ion catalyst. The key feature of the reaction sequence is the cleavage of the Si−Si bond in a 1,3‐silyl shift from silicon to carbon. A central intermediate of the catalysis was structurally characterized by X‐ray diffraction, and the computed reaction mechanism is fully consistent with the experimental findings.