Pyridine → Benzyl 2-azido-2,4-dideoxy-4-fluoro-3,6-di-O-pivaloyl-beta-D-mannopyranoside

HRID 1948829Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1948829
N1C=CC=CC=1.FC(F)(F)S(OS(C(F)(F)F)(=O)=O)(=O)=O.[F:22][C@@H:23]1[C@@H:36]([CH2:37][O:38][C:39](=[O:44])[C:40]([CH3:43])([CH3:42])[CH3:41])[O:35][C@@H:26]([O:27][CH2:28][C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[C@H:25](O)[C@H:24]1[O:46][C:47](=[O:52])[C:48]([CH3:51])([CH3:50])[CH3:49].[N-:53]=[N+:54]=[N-:55].[Na+].[Cl-].[NH4+].[NH4+].[NH4+].[NH4+].[Cl-].[Cl-].[Cl-]>ClCCl>[N:53]([C@H:25]1[C@@H:24]([O:46][C:47](=[O:52])[C:48]([CH3:51])([CH3:50])[CH3:49])[C@H:23]([F:22])[C@@H:36]([CH2:37][O:38][C:39](=[O:44])[C:40]([CH3:43])([CH3:42])[CH3:41])[O:35][C@H:26]1[O:27][CH2:28][C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)=[N+:54]=[N-:55]

Komponenten

7

Edukt 5

HCID 1049PyridineHCID 33557Sodium AzideHCID 67749Trifluoromethanesulfonic anhydrideHCID 22266888Tetraammonium chlorideHCID 66696768HCID 66696768, Verbindung

Produkt 1

HCID 86600947Benzyl 2-azido-2,4-dideoxy-4-fluoro-3,6-di-O-pivaloyl-beta-D-mannopyranoside

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel3×

Versuchsvorschrift

To a solution of pyridine (22.2 μl, 0.274 mmol) in dichloromethane (370 μl) was added dropwise trifluoromethane-sulfonic anhydride (46 μl, 0.274 mmol) at 0° C., and 15 minutes later, a solution of Compound (21) in dichloromethane (1 ml) was added dropwise to the mixture at 0° C. Disappearance of the material was continued by TLC, and the reaction mixture was diluted with dichloromethane. The organic layer was washed with a saturated aqueous solution of sodium hydrogencarbonate, saturated sodium chloride aqueous solution and water, dried over anhydrous magnesium sulfate and thereafter concentrated. The residue was further dried by a vacuum pump, and then dissolved in benzene (1 ml). Sodium azide (13 mg, 0.206 mmol) and tetraammonium chloride (57 mg, 0.206 mmol) were added to the solution under an argon stream at room temperature, and the mixture was reacted at 40° C. The disappearance of the material was confirmed by TLC, and the reaction mixture was thereafter concentrated in a vacuum. The residue was subjected to extraction with ethyl acetate, and the extract was washed with a saturated sodium chloride aqueous solution and water, dried over anhydrous magnesium sulfate and thereafter concentrated. The residue was purified by silica gel column chromatography (ethyl acetatae:hexane=1:4), affording Compound (22) (in an amount of 30.4 mg, 95% in yield).

Aufarbeitung

  1. washThe organic layer was washed with a saturated aqueous solution of sodium hydrogencarbonate, saturated sodium chloride aqueous solution and water
  2. dry with materialdried over anhydrous magnesium sulfate
  3. concentrationconcentrated
  4. customThe residue was further dried by a vacuum pump
  5. dissolutiondissolved in benzene (1 ml)
  6. customthe mixture was reacted at 40° C
  7. concentrationthe reaction mixture was thereafter concentrated in a vacuum
  8. extractionThe residue was subjected to extraction with ethyl acetate
  9. washthe extract was washed with a saturated sodium chloride aqueous solution and water
  10. dry with materialdried over anhydrous magnesium sulfate
  11. concentrationconcentrated
  12. customThe residue was purified by silica gel column chromatography (ethyl acetatae:hexane=1:4)

Quellen und Nachweise

ORD-Eintrag
ord-6588b76ed1224c8695fba0815d781589
Quelldatensatz
uspto-grants-2013_03
Patentnummer
US08399656B2

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