During the optimization process (Supporting information), we identified conditions to selectively generate the 3-hydroxyimine 1b by performing the reaction in chloroform in the presence of molecular sieves. In order to trap the imine intermediate, we carried out a sequential reduction by adding Et2O and 2 eq of NaCNBH3 at 0 ºC. To our delight we found that the reduction took place in a stereoselective manner yielding the syn-1,3aminoalcohol in high yield and with excellent selectivity. Scheme 3 Synthesis of syn-1,3-aminoalcohols via one-pot hydroamination/reduction of propargylic alcohols. The relative stereochemistry was confirmed by coversion to the cooresponding cyclic urethane and analysis of the nOeSY spectra (Supporting Information).