- 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
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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.
- Torssell, K. B. G.,Hazell, A. C.,Hazell, R. G.
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p. 5569 - 5576
(2007/10/02)
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- 2-DEOXY-D-arabino-HEXOSE, 2-DEOXY-D-lyxo-HEXOSE, AND THEIR (2R)-2-DEUTERIO ANALOGS
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A general method for the synthesis of 2-deoxyhexoses is described. 2-Deoxy-D-arabino-hexose and 2-deoxy-D-lyxo-hexose were prepared from D-glucose and D-galactose, respectively, by a route involving reduction of the respective 4,5-O-isopropylidene ketene diethyl dithioacetals with lithium aluminum hydride, followed by removal of the protecting groups.In agreement with the results of earlier studies with ketene dithioacetals of pentose analogs, reduction of the hexose ketene dithioacetals was found to occur both regio- and stereo-specifically.Reduction with lithium aluminum deuteride gave the (2R)-2-deoxy-2-deuterio-hexoses exclusively.
- Wong, Margaret Y. H.,Gray, Gary R.
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