Three-Component Gold(I)-Catalyzed Alkoxyvinylation.

Acetylene has been underexploited despite being a highly valuable feedstock for chemical synthesis. We have developed the first true gold(I)-catalyzed intermolecular three-component reaction between acetylene, alkenes, and alcohols to afford β-vinyl hemiaminal scaffolds from N -vinyl amides. Unusual biscyclopropyl and 3-vinyl N -heterocyclic scaffolds were obtained through the incorporation of a second N -vinyl unit or tethered alkene into the starting material.