With these optimized conditions in hand, we explored the scope and limitations of the asymmetric reaction between 1, 2a and different alcohols 3a-3p (Scheme 2). Enantiopure (S)-2phenylethanol (3b) afforded compound 4ab in good yield and diastereoselectivity (70% and 95:5 dr, respectively). Switching to tertiary alcohols, tert-butanol (3c) gave 4ac in 72% yield and 96:4 er. Tert-amyl alcohol (3d) afforded the corresponding propargylic ether 4ad in good yield (70%) and selectivity (94:6 er). The presence of an arene in the aliphatic chain (3e-g) was tolerated, yielding products 4ae-g in 43-65% yield with 97:3-98:2 er. Cyclic alcohol 3h gave 4ah in 55% yield and 95:5 er. The use of adamantyl-substituted alcohols deserves a special attention since this structure can be found in pharmaceuticals. In our case, trifluoromethylated propargylic ethers 4ai and 4aj containing adamantyl substituents were obtained in good yield and enantioselectivity. Conditions: a The reactions were performed with 0.15 mmol of 2a. The active chiral complex was formed mixing the Cu(I) catalyst with L1 or L2 in the reaction solvent during 1 h. The yield was determined by F-NMR using 1 equiv of PhCF3 as internal standard. The enantiomeric ratio (er) was determined by chiral HPLC. b Isolated yield at 0.20 mmol scale is indicated in brackets.