Reaktion #308198

Reaktionsgleichung

sodium hydrogen carbonate

6-fluoropyridine-3-boronic acid

1-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-3-(5-bromo-2-thienylmethyl)-4-chlorobenzene

cesium fluoride

→

1-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-4-chloro-3-(5-(6-fluoro-3-pyridyl)-2-thienylmethyl)benzene

Ausbeute 88.5%

Lösungsmittel

1,2-dimethoxyethane

Reaktionsbedingungen

Aufarbeitung

1. 1
   workup.ADDITIONadded
2. 2
   TemperaturThe mixture was heated
3. 3
   Temperaturunder reflux for 30 minutes
4. 4
   Extraktionthe mixture was extracted with ethyl acetate
5. 5
   WaschenThe extract was washed with brine
6. 6
   Trocknendried over magnesium sulfate
7. 7
   Sonstigethe solvent was evaporated under reduced pressure
8. 8
   SonstigeThe residue was purified by silica gel column chromatography (hexane:ethyl acetate=75:25-60:40)

Vorschrift

1-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-3-(5-bromo-2-thienylmethyl)-4-chlorobenzene 71 (500 mg) obtained in Example 128-(4) was dissolved in 1,2-dimethoxyethane (15 ml), and added thereto were 6-fluoropyridine-3-boronic acid 58 (228 mg), tetrakis(triphenylphosphine)palladium(0) (94 mg) and cesium fluoride (738 mg). The mixture was heated under reflux for 30 minutes. The reaction solution was poured into a saturated aqueous sodium hydrogen carbonate solution and the mixture was extracted with ethyl acetate. The extract was washed with brine and dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (hexane:ethyl acetate=75:25-60:40) to give 1-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-4-chloro-3-(5-(6-fluoro-3-pyridyl)-2-thienylmethyl)benzene (454 mg) as a colorless solid. APCI-Mass m/Z 634/636 (M+H). (2) The above 1-(2,3,4,6-tetra-O-acetyl-β-Dglucopyranosyl)-4-chloro-3-(5-(6-fluoro-3-pyridyl)-2-thienylmethyl)benzene was treated in a manner similar to Example 106-(3) to give the desired 1-(β-D-glucopyranosyl)-4-chloro-3-(5-(6-fluoro-3-pyridyl)-2-thienylmethyl)benzene as colorless powder. APCI-Mass m/Z 483 (M+NH4), 466 (M+H).

Quelle