Copper (I)‐BOX Catalyzed Asymmetric 3‐Component Reaction for the Synthesis of Trifluoromethylated Propargylic Ethers and Anilines**

An asymmetric 3-component reaction between EthynylBenziodoXoles (EBXs), 2,2,2-trifluorodiazoethane and nucleophiles catalyzed by a CuI-BOX (Bisoxazoline) catalyst is described. This protocol gives access to chiral trifluoromethylated propargyl ethers and anilines, which are valuable building blocks in synthetic and medicinal chemistry. The reaction proceeds with high enantioselectivity and yield with different nucleophiles such as primary, secondary and tertiary alcohols, as well as both electron-rich and electron-poor anilines. Aryl-, alkyl- and silyl-substituted alkynes can be successfully introduced as electrophiles. In case of chiral substrates, high catalyst control was observed, leading to good diastereoselectivity.