A novel method for the preparation of alkyl azides from alcohols by way of oxidation-reduction condensation is described. According to this reaction, the sterically hindered tert-alkyl phosphinites that are prepared from the corresponding alcohols are converted into tert-alkyl azides with almost complete inversions of their stereochemistries. On treatment with LiAlH4 the obtained alkyl azides are then successfully reduced to afford the corresponding amines in good yields, thus, a versatile method for the preparation of chiral amines from the corresponding chiral alcohols was established.