Development of a protecting group for sulfate esters

Tetrahedron Letters

Volumn 38, Issue 41, 1997, Pages 7243-7246

  Proud, Andrew D ^c   Prodger, Jeremy C ^b   Flitsch, Sabine L ^a  

^a UNIVERSITY OF EDINBURGH   (United Kingdom)

^b GLAXOSMITHKLINE   (United Kingdom)

^c NONE

Author keywords

[No Author keywords available]

Indexed keywords

SUGAR;

ARTICLE; CARBOHYDRATE SYNTHESIS; DRUG PURIFICATION; IN VITRO STUDY; MASS SPECTROMETRY; METHODOLOGY; REACTION ANALYSIS;

EID: 0030692125     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)01681-X     Document Type: Article

References (13)

1. Kaiser, E. T. The Organic Chemistry of Sulfur; Oae, S.; Plenum Press: New York and London, 1944; pp. 48-74.
2. Penney, C.L.; Perlin, A.S. Carbohydr. Research 1981, 93, 241-246.
3. Meese, C. O. Synthesis 1984, 1041-1042.
4. Ho, J.; Fishbein, J. C. J. Am. Chem. Soc. 1994, 116, 6611-6621.
5. Preparation of 2,2,2-trifluorodiazoethane: CAUTION:-This compound is potentially explosive and must be considered as highly toxic. All experiments using this reagent were carried out in glassware with Clear-Seal joints and behind blast screens:-Sodium Nitrite (3.0g, 1eq) in water (10ml) was added to a solution of 2,2,2-trifluoroethylamine hydrochloride (5.4g, 1eq) in water (20ml) at 0°C. A stream of Nitrogen gas was bubbled through the liquid, the mixture of gas and 2,2,2-trifluorodiazoethane was passed over KOH pellets before being trapped in acetonitrile (40ml) at -40°C. After Ihr at 0°C the aqueous mixture was warmed to room temp over 1hr. The solution of 2,2,2-trifluorodiazoethane was used without further purification.
6. 4) and the solvent removed in vacuo. The product was purified by column chromatography.
7. General sulfation method:-The sugar (1.0eq) and pyridine/sulfur trioxide complex (1.0-5.0eq) were heated (80°C) in acetonitrile until no starting material remained (1-2 hrs).
8. Guilbert, B.; Davis, N. J.; Pearce, M.; Aplin, R. T.; Flitsch, S. L. Tetrahedron: Asymmetry 1994, 5, 2163-2178.
9. Langston, S.; Bernot, B.; Vasella, A. Helv. Chim. Acta. 1994, 77, 2341-2353.
10. 9S requires 445.07802, found 445.07860.
11. General method for deprotection of trifluoroethylsulfate esters:-Substrate (10mg, 1eq) was dissolved in tert butyl alcohol, potassium tert butoxide (5eq) was added and mixture refluxed until reaction was complete (1-2hrs). The product was purified by column chromatography.
12. Mumma, R. O.; Hoiberg, C.P.; Simpson, R. Carbohydr. Res. 1970, 14, 119-121.
13. Lupescu, N.; Arad, S.; Geresh, S.; Bernstein, M. A.; Glaser, R. Carbohydr. Res. 1991, 210, 349-352.