General Zinc‐Catalyzed Intermolecular Hydroamination of Terminal Alkynes

Abstract
Catalytic hydroaminations are one of the most sustainable CN bond‐forming processes as a result of 100 % atom economy and the availability of substrates. Here, it is shown that the intermolecular hydroamination of terminal alkynes with anilines proceeds smoothly in the presence of catalytic amounts of zinc triflate, an easily available and inexpensive zinc salt. Amination and subsequent reduction with NaBH3CN gives a variety of secondary and tertiary amines in up to 99 % yield and with over 99 % Markovnikov regioselectivity. Moreover, difficult functional groups such as nitro and cyano substituents are tolerated by the homogeneous catalyst.