Gold-Catalyzed Intermolecular Assembly of Donor and Acceptor Fragments for [1,5]-Hydride Migrations

The [1,n]-hydride migration reactions represent one of the most powerful techniques to functionalize C(sp3)–H bonds and to rapidly construct molecular complexities. However, their substrates usually required multiple steps to prepare in advance. Herein, we developed a gold-catalyzed intermolecular coupling of hydride-donor-containing nucleophiles (amines) and hydride-acceptor-containing alkynes (1,3-diynamides) for cascade [1,5]-hydride migrations. Control experiments revealed the role of the dichloroethane solvent and the unexpected involvement of protonated anilines in promoting [1,5]-hydride migrations.