Enamine Synthesis via Regiocontrolled 6‐<i>endo</i>‐<i>dig</i> and 5‐<i>exo</i>‐<i>dig</i> Tethered Carboamination of Propargylic Alcohols

Enamines are versatile building blocks for the synthesis of biologically active compounds. Nevertheless, only a limited number of strategies have been reported for preparing trisubstituted enamines in a regio- and stereoselective manner. Herein, we report a regiocontrolled 6-endo and 5-exo tethered carboamination of propargylic alcohols for the synthesis of trisubstituted enamines. High regioselectivity was achieved through fine-tuning of the amine protecting group during the Pd-catalyzed carboamination. The introduced trifluoromethylated tether enables further stereoselective functionalizations, such as hydrogenation and fluorination.