Total Asymmetric-Synthesis of 3-Deoxy-Hexoses and 4-Deoxy-Hexoses and Derivatives

(1S,4S)-7-Oxabicyclo[2.2.1]hept-5-en-2-one ((-)-5, a "naked sugar") has been converted to (-)-(1R,4S,6S)-6-endo-benzyloxy-2-bromo-7-oxabicyclo[2.2.1]hept-2-ene ((-)-12) in a highly stereoselective fashion. Double hydroxylation of the C=C double bond of (-)-12, followed by acetylation and Baeyer-Villiger oxidation of the resulting alpha-acetoxyketone (-)-14 afforded (-)-5-O-acetyl-2-O-benzyl-3-deoxy-beta-D-arabino-hexofuranurono-6,1-lact one ((-)-15). This compound was converted readily into (+)-methyl 3-deoxy-alpha-D-arabino-hexofuranoside ((+)-6) and (+)-methyl 3-deoxy-beta-L-xylo-hexofuranoside ((+)-7) and partially protected derivatives. (-)-15 was also converted into 4-deoxy-D-lyxo-hexopyranose (34) and several partially protected derivatives such as (+)-methyl 4-deoxy-2,3-O-isopropylidene-alpha-D-lyxo-hexo-pyranoside ((+)-8).


Published in:
Tetrahedron, 48, 48, 10587-10602
Year:
1992
ISSN:
0040-4020
Keywords:
Note:
Univ lausanne,chim sect,2 rue barre,ch-1005 lausanne,switzerland.
Laboratories:




 Record created 2005-11-09, last modified 2018-03-17


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