Regio- and Stereoselective Hydroamination of Alkynes Using an Ammonia Surrogate: Synthesis of N‑Silylenamines as Reactive Synthons

An anti-Markovnikov selective hydroamination of alkynes with N-silylamines to afford N-silylenamines is reported. The reaction is catalyzed by a bis­(amidate)­bis­(amido)­Ti­(IV) catalyst and is compatible with a variety of terminal and internal alkynes. Stoichiometric mechanistic studies were also performed. This method easily affords interesting N-silylenamine synthons in good to excellent yields and the easily removable silyl protecting group enables the catalytic synthesis of primary amines.