Stereospecific Nucleophilic Substitution of Enantioenriched Tertiary Benzylic Amines via in Situ Activation with Benzyne

A one-pot protocol has been developed for sequential benzyne activation and nucleophilic substitution of enantioenriched tertiary benzylic amines. In the presence of 2 (trimethylsilyl)phenyl triflate and CsF, a range-of enantioen-riched tertiary benzylic amines were substituted by various nucleophiles, delivering structurally diverse benzylic-compounds in moderate to excellent yields with excellent retention of enantiopurity. Importantly, this operationally simple protocol permitted formation of various chiral C-S, C-Se, C-C, and C-N bonds with excellent enantiopurity under metal-free conditions.