SILYL NITRONATES AND NITRILE OXIDES IN ORGANIC SYNTHESIS. A NOVEL ROUTE TO D,L-DEOXYSUGARS. USE OF ALUMINIUM OXIDE AS SOLID PHASE BASE FOR GENERATION OF NITRILE OXIDES FROM HYDROXIMIC ACID CHLORIDES

Article abstract of DOI:10.1016/S0040-4020(01)91358-4

Novel methodology is developed for a three step synthesis of deoxyaldoses and deoxyketoses. 1.Regioselective addition of silyl nitronate or nitrile oxide to a diene. 2.Stereospecific hydroxylation of the double bond. 3.Unmasking of the aldol moiety by catalytic reduction of the 2-isoxazoline.The syntheses of D.L-deoxyribose, D,L-oleose, D,L-digitoxose, D,L-2-deoxygalactose, 1,3-dideoxyfructose, 3-deoxyfructose etc. are described.Basic aluminium oxide is introduced as a solid phase base for the one step synthesis of 2-isoxazolines from aldoximes and olefins.An X-ray diffraction study of compound 13c verifies the stereochemical assignments.