Phytosphingosines - A facile synthesis and spectroscopic protocol for configurational assignment

Article abstract of DOI:10.1016/S0040-4020(99)00839-X

A facile synthesis of four of the eight configurational isomers of phytosphingosine has been performed by employing Wittig and Julia olefination followed by Sharpless dihydroxylation. The set of these four stereoisomers served as model compounds for developing general chemical/CD/NMR protocols for assigning relative and absolute configurations of all phytosphingosine isomers. The procedure is based on a two-step derivatization to 2-N- naphthimide-1,3,4-0-trinaphthoate derivatives which gives rise to unique exciton coupled circular dichroic and 'H-NMR spectra in selected solvents. The spectra can be used as reference data for assignment of relative as well as absolute configurations of phytosphingosine isomers and congeners at the low-nanomole level.