Several 1,1′-bi-2-naphthol (BINOL)-based Schiff bases were prepared from the condensation of (R)-3,3′-diformyl BINOL with chiral benzylic amine derivatives. These compounds were used to catalyze the reaction of phenylacetylene with aldehydes in the presence of ZnEt2 with up to 85% ee and 83% yield.3,3′-Bis{[((S)-1-phenylethyl)imino]methyl}-(R)-[1,1′-binaphthalene]-2,2′-diolC38H32N2O2De >99% (NMR)[α]D20=+168.3 (c 1.0, CHCl3)Source of chirality: (R)-1,1′-bi-2-naphthol and (S)-1-phenylethylamineAbsolute configuration: (R,S,S)3,3′-Bis{[((R)-1-phenylethyl)imino]methyl}-(R)-[1,1′-binaphthalene]-2,2′-diolC38H32N2O2De >99% (NMR)[α]D20=-20 (c 1.0, CHCl3)Source of chirality: (R)-1,1′-bi-2-naphthol and (R)-1-phenylethylamineAbsolute configuration: (R,R,R)3,3′-Bis{[((S)-1,2,3,4-tetrahydronaphthalen-1-yl)imino]methyl}-(R)-[1,1′-binaphthalene]-2,2′-diolC42H36N2O2De >99% (NMR)[α]D20=+36.6 (c 1.0, CHCl3)Source of chirality: (R)-1,1′-bi-2-naphthol and (S)-1,2,3,4-tetrahydronaphthalen-1-yl amineAbsolute configuration: (R,S,S)3,3′-Bis{[((S)-1-(naphthalen-2-yl)ethyl)imino]methyl}-(R)-[1,1′-binaphthalene]-2,2′-diolC46H36N2O2De >99% (NMR)[α]D20=+328.4 (c 1.0, CHCl3)Source of chirality: (R)-1,1′-bi-2-naphthol and (S)-1-(naphthalen-2-yl)ethyl amineAbsolute configuration: (R,S,S)