Next, we move to the study of anilines as nucleophiles (Scheme 4) considering our previous work on the racemic process. We chose as a model the reaction between 1, 2a and methyl 4-aminobenzoate (11a). Unfortunately, despite the good er obtained (98:2); the desired product (12aa) was obtained in only 66% yield with low reproducibility using the conditions optimized for alcohols. After screening of different BOX ligands, Cu(I) catalysts, solvents, concentrations and temperatures, L2 in combination with the cationic complex formed between CuCl/AgNTf2 in DCE at room temperature afforded compound 13aa in good yield (71%) and good enantioselectivity (94:6 er) with high reproducibility (See Supporting Information for further details on reaction optimization). When reagent 2d was submitted to the re-optimized conditions, compound 13da was obtained in 52% yield and 86:14 er. Alkyl substitution was also well tolerated on the alkyne. Both cyclopropyl (c-Pr) and tert-butyl (t-Bu)substituted alkynes gave products 13ea and 13fa in 71% yield and 91:1 er and 64% yield and 94:6, respectively. Thiophene substituted alkyne 13ga was obtained in 65% yield and 91:9 er. The scope of substituted anilines was then explored. Electron withdrawing groups, such as trifluoromethyl or para-fluoro gave the desired products 13ab and 13ac 27 in similar yield and selectivity. 1,2,3,4-Tetrahydroquinoline afforded compound 13ad in moderated yield and good enantioselectivity. The presence of a methyl or methoxy in para position led to lower enantioselectivity (products 13ae and 13af). We also examined phenols and carboxylic acids as nucleophiles (Scheme 5A). In this case, the combination of Cu(MeCN)4SbF6 and an excess of the nucleophile afforded the best results. In the case of phenols 14a and 14b, compounds 15a and 15b were obtained in good yield and moderate selectivity. In contrast, using 2-cyclohexanecarboxylic acid (16), we were able to reach good enantioselectivity for ester 17, but the reaction did not go to completion.