Stereoselective synthesis of 1,2-cis- and 2-deoxyglycofuranosyl azides from glycosyl halides.
Protected 1,2-cis glycofuranosyl azides with alpha-D-ribo, beta-D-arabino and 2-deoxy-2-fluoro-beta-D-arabino configurations were efficiently prepared from the appropriate 1,2-trans glycosyl halides bearing non-participating 0-2 substituent by inversion with sodium azide under phase transfer catalytic conditions (80-85% yields, 90-96% de). The same method failed to result in sufficiently good beta-selectivity starting from 2-deoxy-3,5-di-O-(p-toluoyl)-alpha-D-ery-thro-pentofuranosyl chloride (5alpha) (40% de). The selectivity in favour of the protected 2-deoxy-beta-D-erythro-pentofura-nosyl azides was greatly improved (74-80% de) by treating 5alpha and its p-chlorobenzoyl analog 6alpha with cesium or potassium azide in dimethylsulfoxide at room temperature (83-85% yields).
Stimac
A
A
National Institute of Chemistry, Ljubljana, Slovenia.
Kobe
J
J
D001386:Azides / Q000138:chemical synthesis* / Q000737:chemistry; D002236:Carbohydrate Conformation; D015394:Molecular Structure; D013237:Stereoisomerism
D001386:Azides