SYNTHESIS OF THE HYDROXYAMINO SUGAR OF CALICHEAMICINS

Methyl 6-deoxy-2,3-0-isopropylidene-4-0-mesyl-alpha-D-galactopyranoside (6) was prepared from D-galactose in six steps. 6 was subjected to a nucleophilic displacement reaction with sodium azide as the nucleophile to yield methyl 4-azido-4,6-dideoxy-2,3-0-isopropylidene-alpha-D-glucopyranoside (7) in...

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Bibliographic Details
Published inLiebigs Annalen der Chemie no. 2; pp. 117 - 120
Main Authors RAINER, H, SCHARF, HD
Format Journal Article
LanguageEnglish
Published DEERFIELD BEACH Wiley 12.02.1993
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
CALICHEAMICINS
OLIGOSACCHARIDE
CALICHEMICINS
ANTICANCER AGENTS
DNA
CARBOHYDRATES
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Summary:Methyl 6-deoxy-2,3-0-isopropylidene-4-0-mesyl-alpha-D-galactopyranoside (6) was prepared from D-galactose in six steps. 6 was subjected to a nucleophilic displacement reaction with sodium azide as the nucleophile to yield methyl 4-azido-4,6-dideoxy-2,3-0-isopropylidene-alpha-D-glucopyranoside (7) in 75% yield. Reduction of the azido group with NaBH, afforded the amino sugar 8 (81%) which was adsorbed on silica gel and subsequently oxidized with ozone to methyl 4,6-dideoxy-2,3-0-isopropylidene-4-nitro-alpha-D-glucopyranoside (10, 80%). This crystalline and stable compound 10 was reduced with Zn/NH4Cl to yield the desired methyl 4,6-dideoxy-4-hydroxy-amino-2,3-0-isopropylidene-alpha-D-glucopyranoside (11, 85%), which is unstable to air and therefore has to be transferred to its N,O-diacetate derivate 12. No chromatographic purification was necessary.
ISSN:0170-2041
DOI:10.1002/jlac.199319930121