(Diethylamino)sulfur trifluoride → HCID 53672498, compound

HRID 233557Notes

Reaction equation

HRID 233557 reaction equation
C(N(S(F)(F)[F:7])CC)C.[C:10]([NH:13][C@H:14]1[C@@:23](C(=O)C2C=CC=CC=2)([OH:24])[C@:22](C(=O)C2C=CC=CC=2)([OH:33])[C@@H:21]([CH2:42]O)[O:20][C@@H:15]1[O:16][CH2:17][CH:18]=[CH2:19])(=[O:12])[CH3:11]>COCCOCCOC.C[O-].[Na+].CO>[C:10]([NH:13][C@H:14]1[C@@H:23]([OH:24])[C@H:22]([OH:33])[C@@H:21]([CH2:42][F:7])[O:20][C@@H:15]1[O:16][CH2:17][CH:18]=[CH2:19])(=[O:12])[CH3:11]

Participants

6

Reactant 2

HCID 123472(Diethylamino)sulfur trifluorideHCID 53752233HCID 53752233, compound

Product 1

HCID 53672498HCID 53672498, compoundYield 99%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 8150DiglymeSolvent2×HCID 10942334Sodium MethoxideSolvent

Conditions

Temperature
40 °C

Procedure

To a stirred solution of (diethylamino)sulfur trifluoride (0.5 mL) in dry diglyme (2mL) was added a solution of allyl 2-acetamido-3,4-di-benzoyl-2-deoxy-α-D-mannopyranoside, prepared as described above, (100 mg) in dry diglyme (3 mL) at room temperature, and the reaction mixture was stirred for one hour at room temperature and three hours at 40° C. After the starting material was consumed, the reaction mixture was poured onto ice-water and extracted with ethyl acetate. The extract was dried, concentrated, and the residue was applied to silica gel chromatography. After the impurity was eluted with hexane, the product was eluted with ether to give the fluorinated product in 89 percent yield. The product was then dissolved in 5 mL of 1N sodium methoxide in methanol to remove benzoyl group. After 20 minutes, Dowex 50W X-8[H+ ] was added to neutralize the reaction mixture. The resin was filtered and the filtrate was concentrated to give allyl 2-acetamido-2,6-dideoxy-6-fluoro-α-D-mannopyranoside in 99 percent yield. The product (50 mg), 1.2 equivalents of palladium (II) acetate, and 2.5 eq of sodium acetate in 95 percent acetic acid (5 mL) were stirred at 50° C. for 18 hours, and the solvent was removed under vacuum. The residue was applied to silica gel chromatography, eluted with ethyl acetate/methanol (2/1) to obtain 2-acetamido-2,6-di-deoxy-6-fluoro-α-D-mannopyranoside in 73 percent yield.

Workup

  1. customprepared
  2. customat room temperature
  3. customAfter the starting material was consumed
  4. additionthe reaction mixture was poured onto ice-water
  5. extractionextracted with ethyl acetate
  6. customThe extract was dried
  7. concentrationconcentrated
  8. washAfter the impurity was eluted with hexane
  9. washthe product was eluted with ether
  10. customto give the fluorinated product in 89 percent yield
  11. customto remove benzoyl group
  12. waitAfter 20 minutes
  13. additionDowex 50W X-8[H+ ] was added
  14. filtrationThe resin was filtered
  15. concentrationthe filtrate was concentrated

Sources & evidence

ORD record
ord-4c948e9674d144faa79b11e607c9d007
Source dataset
uspto-grants-1997_01
Patent number
US05593887

Reaction notes

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