Cobalt-Hydride-Catalyzed Hydrosilylation of 3‑Alkynes Accompanying π‑Bond Migration

We describe a protocol for cobalt-catalyzed hydrosilylation of 3-alkynes with accompanying π-bond migration. Mechanistic studies indicate that (i) cobalt­(I)-hydride bearing a bulky bisphosphine ligand is the key intermediate and (ii) π-bond migration occurs prior to hydrosilylation. The cascade process selectively furnishes terminal branched allylsilanes under mild conditions.