Preparative syntheses of 2,6-dideoxy-alpha-L-lyxo-hexose (2-deoxy-alpha-L-fucose) and its D-ribo epimer (digitoxose).
Methyl 4,6-O-benzylidene-2-deoxy-alpha-D-ribo-hexopyranoside (1) is converted into methyl 3,4-di-O-benzoyl-6-bromo-2,6-dideoxy-alpha-D-ribo-hexopyranoside (3) via the 3-O-benzoyl derivative (2) of 1 by subsequent treatment with N-bromosuccinimide. Compound 3 is the key intermediate in high-yielding, preparative syntheses of the title dideoxy sugars, which are constituents of many antibiotics, Dehydrohalogenation of 3 affords the 5,6-unsaturated glycoside 7, which undergoes stereospecific reduction by hydrogen with net inversion at C-5 to give methyl 3,4-di-O-benzoyl-2,6-dideoxy-beta-L-lyxo-hexopyranoside (8), whereas reductive dehalogenation of 3 provides the corresponding D-ribo derivative 4. The unprotected glycosides 9 (L-lyxo) and 5 (D-ribo) are readily obtained by catalytic transesterification, and mild, acid hydrolysis gives the crystalline title sugars 10 (L-lyxo) and 6 (D-ribo) in 45 and 57% overall yield from 1 without the necessity of chromatographic purification at any of the steps.
D055598:Chemical Phenomena; D002621:Chemistry; D003630:Daunorubicin / Q000031:analogs & derivatives; D003837:Deoxy Sugars / Q000138:chemical synthesis*; D004317:Doxorubicin / Q000031:analogs & derivatives; D005643:Fucose / Q000031:analogs & derivatives* / Q000138:chemical synthesis; D006601:Hexoses / Q000138:chemical synthesis*
D003837:Deoxy Sugars; D006601:Hexoses; D005643:Fucose; D004317:Doxorubicin; D003630:Daunorubicin