AuI‐Catalyzed Direct Hydroamination/Hydroarylation and Double Hydroamination of Terminal Alkynes

Abstract An efficient method for formal Markownikoff hydroamination/hydroarylation and double hydroamination of terminal alkynes has been developed. For example, treatment of terminal alkynes with amino‐aromatics or diamines in the presence of 2–5 mol‐% of Ph 3 PAuNTf 2 in toluene at 100 °C gave the corresponding products in excellent yields. The method was shown to be applicable to a broad range of substrates and, more importantly, unlike our previously reported method, a tethered hydroxy group in the alkyne is not necessary. The mechanism of the reaction is also discussed.