Hydroboration of aliphatic 1-alkynes with freshly prepared dicyclohexylborane (1 mol-equiv., hexane), treatment of the resulting [(E)-1-alkenyl]boranes 5 with Et2Zn or Me2Zn (1.05 mol-equiv.) followed by addition of (−)-3-exo-(dimethylamino)isoborneol (DAIB, 8; 0.01 mol-equiv.), subsequent addition of a solution of an aromatic or aliphatic aldehyde (1 mol-equiv., hexane), and quenching with aq. NH4Cl provided (E)-allyl alcohols 6 usually in 70–95% yield with 79–98% enantiomeric excess (Scheme 3 and Table).