Chemoenzymatic stereoconvergent synthesis of 3-O-benzoyl azidosphingosine

• Published in: Tetrahedron: Asymmetry
• Main Authors: Compostella, F, Franchini, F, Giovenzana, G. B, Panza, L, PROSPERI, DAVIDE, Ronchetti, F.
• Other Authors: Giovenzana, G, Prosperi, D, Ronchetti, F
• Format: Article in Journal/Newspaper
• Language: English
• Published: Pergamon 2002
• Subjects: sintesi organica; reazioni enzimatiche; BIO/10 - BIOCHIMICA; Antarc*; Antarctica
• Online Access: http://hdl.handle.net/10281/24682; 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