De Novo Synthesis of Oligosaccharades Using a Palladium-Catalyzed Glycosylation Reaction

Journal of the American Chemical Society

Volumn 126, Issue 11, 2004, Pages 3428-3429

  Babu, Ravula Satheesh ^a   Zhou, Maoquan ^a   O'Doherty, George A ^a  

^a WEST VIRGINIA UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

2,3 DIDEOXYOLIGOSACCHARIDE DERIVATIVE; OLIGOSACCHARIDE; PALLADIUM; UNCLASSIFIED DRUG;

ARTICLE; CARBOHYDRATE SYNTHESIS; CATALYSIS; CHEMICAL STRUCTURE; DIHYDROXYLATION; GLYCOSYLATION; METAL BINDING; OLIGOSACCHARIDE SYNTHESIS; PRODUCT RECOVERY; REACTION ANALYSIS; REACTION OPTIMIZATION; REDUCTION; STRUCTURE ANALYSIS;

CARBOHYDRATE SEQUENCE; CATALYSIS; GLYCOSYLATION; MOLECULAR SEQUENCE DATA; OLIGOSACCHARIDES; PALLADIUM; PYRANS; RHAMNOSE;

EID: 1642342224     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja039400n     Document Type: Article

References (22)

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9. While the diastereoselective transfer of a pyranone ring to an alcohol is an uncommon glycosylation reaction because the pyranone ring is at the same oxidation state as a traditional sugar (one OH per carbon atom), we feel this transfer of a bis-anhydro-sugar is as much a glycosylation reaction as other common glycosylation reactions (e.g. the transfer of a deoxysugar).
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13. Important to the successful execution of this process, both reactions must occur with virtually complete diastereocontrol.
14. While the dihydroxylation products were easily purified by silica gel chromatography, no efforts were taken to detect for trace levels of osmium.
15. For glycosylation at the C-4 position we found that the best yields were obtained when a 2:1 ratio of glycosyl donor to acceptor was used.
16. Not surprisingly, the glycosylation reaction consistently occurs in higher yields with the substrates having the smaller C-6 methyl substituents.
17. The Pd-catalyzed glycosylation was significantly slower and occurred in lower yields (14a to 15a and 16a to 17a), when using a pyranone with a C-1 pivaloate-leaving group.
18. Using a different retrosynthetic bond disconnection, Sinou used a palladium-allylation reaction to prepare 1,4-disaccharides, see: Sinou, D.; Frappa, I.; Lhoste, P.; Porwanski, S.; Kryczka, B. Tetrahedron Lett. 1995, 36, 1251-1254.
19. To demonstrate the generality of this process we prepared 18b, 20b, 23b and 24b in the all D-enantiomeric form.
20. For a related alterative approach to 2-deoxysugars, see: (a) McDonald, F. E.; Reddy, K. S.; Diaz, Y., J. Am. Chem. Soc. 2000, 122, 4304-4309.
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22. We have found o-nitrophenylsulfonylhydrazide/triethylamine to be an excellent diimide precursor, ideal for reducing pyrans of this type, see: Haukaas, M. H.; O'Doherty, G. A. Org. Lett. 2002, 4, 1771-1774.