A PhI(OAc)2-mediated trifluoromethylthiolation/oxidative cyclization of ynamides with Shen reagent has been established herein, providing a facile access to CF3S-substituted oxazolidine-2,4-diones bearing a quaternary carbon center in 38~85% yields with chemo-selectivities...

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A chemo‐selective copper(I)‐catalyzed oxytrifluoromethylation of N‐Boc‐ynamides with TMSCF3 has been achieved, affording the trifluoromethylated oxazolones in 51–99% yields. The reaction proceeds at room temperature and tolerates a variety of functional groups such as −X, −OMe, alkenyl, and other substituents. The resulting oxazolones provide access to α‐CF3‐substituted amines through decarboxylative reduction.