In summary, we have developed the first asymmetric enantioselective 3-CR between hypervalent iodine reagents, 2,2,2trifluorodiazoethane (1) and nucleophiles using a Cu(I) catalyst. Tertiary, secondary and primary alcohols as well as electron-rich and electron-poor anilines can be used as nucleophiles affording fluorinated propargylic ethers and anilines in up to 99:1 er. Alkyl-, aryl-and silyl-substituted EBxs could be used in the process, giving access to structurally diverse alkynes. With chiral substrates, high catalyst control was observed leading to high diastereoselectivity.