Atom‐Economical and Stereoselective Difunctionalization of Electron‐Withdrawing Alkynes with N ‐Trifluoromethylthiophthalimide

An N ‐methylmorpholine‐catalyzed aminotrifluoromethylthiolation of electron‐withdrawing alkynes leads to α,β‐unsaturated esters bearing a nitrogen and SCF 3 groups. Here, N ‐trifluoromethylthiophthalimide serves as both the nitrogen and the SCF 3 source. This difunctionalization reaction features mild reaction conditions, high atom economy, good yield (up to 93%) and excellent stereoselectivity ( Z / E up to 28 : 1). This study provides a versatile approach for the synthesis of −SCF 3 ‐containing molecules (i. e. α‐SCF 3 ‐β‐amino acids).