Au → M bonds promote catalytic alkyne hydrofunctionalisation

The impact of metalloligands on Au catalysed alkyne hydrofunctionalisation is studied. Ambiphilic PMP-type ligands (M = CuI, AgI, ZnII) stabilise Au → M bonds including unprecedented AuI → ZnII interactions. The Lewis acidity of Au increases in the order CuI < AgI < ZnII promoting catalytic cycloisomerisation of propargylamide 14. Au/Zn complex 8 is an excellent catalyst for alkyne hydroamination.