We describe a novel stereoselective total synthesis of d-ribo-[1,1- 2 H-1,2- 1 3 C]phytosphingosine (12). Chirality at the incipient C-4 position was derived from asymmetric dihydroxylation of 1-hexadecene. The remaining chiral centers were formed by Sharpless epoxidation of an allylic alcohol, followed by benzoylcarbamate cyclization to furnish a 2-amino-1,3,4-triol derivative with the desired stereochemistry. The 2 H and 1 3 C labels were introduced by Horner-Emmons condensation of 1 3 C-labeled triethyl phosphonoacetate, followed by reduction of the resulting carboxylic ester with AlCl 3 /LiAlD 4 . Mass spectral results indicated the suitability of 12 as an internal standard for analyses by the isotope dilution method.