It is known that the main mode of synthesis of doxylamine is a racemic mixture. However, the active enantiomers of the compound show superior activity to that of the racemate, thus the need to synthesize doxylamine as an enantiopure compound. This study aimed to synthesise an enantiopure (d)-doxylamine and it was achieved through the use of optically active diols synthesised from a novel chiral auxiliary. While most available methods employ Sharpless asymmetric dihydroxylation, this study reports a method that achieves superior enantiomeric excess with consequent better yields of 67% of end products not easily accessible by use of Sharpless Asymmetric Dihydroxylation.