Chemoenzymatic stereoconvergent synthesis of 3-O-benzoyl azidosphingosine

• Published in: Tetrahedron: Asymmetry
• Main Authors: F. Compostella, F. Ronchetti, L. Franchini, G. B. Giovenzana, L. Panza, D. Prosperi
• Other Authors: G.B. Giovenzana
• Format: Article in Journal/Newspaper
• Language: English
• Published: 2002
• Subjects: Settore BIO/10 - Biochimica; Antarc*; Antarctica
• Online Access: http://hdl.handle.net/2434/182029; http://www.scopus.com/inward/record.url?eid=2-s2.0-0037094745&partnerID=40&md5=646d94d4c75b018bf79198baf5c88bd9; https://doi.org/10.1016/S0957-4166(02)00201-X

The synthesis of 3-O-benzoyl azidosphingosine 1 through a stereoconvergent approach is described. Nucleophilic addition of the Grignard reagent of 1-pentadecyne to cyclohexylidene-D-glyceraldehyde results in a mixture of diastereoisomeric propargylic alcohols. Subsequent enzymatic separation of these diastereoisomers, mediated by lipase from Candida antarctica, Mitsunobu inversion on the wrong diastereoisomer and extremely efficient introduction of azide using a chloromesylate leaving group affords the title compound in 30% overall yield.