Hydrochloric Acid → HCID 58786202, compound

HRID 1375985Notes

Reaction equation

HRID 1375985 reaction equation
[CH2:1]([Li])CCC.[F:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1[CH3:13].CC(C)([O-])C.[K+].[CH2:20]([O:27][C@@H:28]1[C@@H:34]([O:35][CH2:36][C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)[C@H:33]([O:43][CH2:44][C:45]2[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=2)[C@@H:32]([CH2:51][O:52][CH2:53][C:54]2[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=2)[O:31]C1=O)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.Cl>C1COCC1.CCCCCC>[CH2:20]([O:27][C@@H:28]1[C@@H:34]([O:35][CH2:36][C:37]2[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=2)[C@H:33]([O:43][CH2:44][C:45]2[CH:46]=[CH:47][CH:48]=[CH:49][CH:50]=2)[C@@H:32]([CH2:51][O:52][CH2:53][C:54]2[CH:55]=[CH:56][CH:57]=[CH:58][CH:59]=2)[O:31][C@H:13]1[C:8]1[CH:9]=[CH:10][CH:11]=[C:12]([CH3:1])[C:7]=1[F:6])[C:21]1[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 72412-FluorotolueneHCID 10907626(3R,4S,5R,6R)-3,4,5-Tris(benzyloxy)-6-((benzyloxy)methyl)oxan-2-oneHCID 23665647Potassium tert-butoxideHCID 178418339Butyllithium

Product 1

HCID 58786202HCID 58786202, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

A 1.56 M n-hexane solution of n-butyl lithium (3.57 ml) and 2-fluorotoluene (0.66 ml) were added in that order to a suspension of potassium t-butoxide (625 mg) in THF (11 ml) at −78° C. and the mixture was stirred at the same temperature for 1.5 hours. A solution of 2,3,4,6-tetra-O-benzyl-D-(+)-glucono-1,5-lactone (3.00 g) in THF (10 ml) was added dropwise to the reaction mixture and the mixture was stirred at the same temperature for 30 minutes. After the addition of a 1 M aqueous solution of hydrochloric acid, the mixture was heated to room temperature. The reaction mixture was extracted with diethyl ether. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. After filtration, the solvent was evaporated under reduced pressure. The filtrate was concentrated and dried to be solid. The resulting residue was dissolved in dichloroethane (5 ml) and acetonitrile (25 ml). Triisopropylsilane (2.27 ml) and boron trifluoride-diethyl ether complex (0.85 ml) were added to the solution at −30° C. After stirring at the same temperature for 30 minutes, saturated aqueous solution of sodium bicarbonate was added to the reaction mixture. The mixture was extracted with diethyl ether. The organic layer was washed with saturated brine and dried over anhydrous sodium sulfate. After filtration, the solvent was evaporated under reduced pressure. The resulting residue was purified by silica gel column chromatography (ethyl acetate-n-hexane) to obtain (1S)-1,5-anhydro-2,3,4,6-tetra-O-benzyl-1-(2-fluoro-3-methylphenyl)-D-glucitol (559 mg).

Workup

  1. stirringthe mixture was stirred at the same temperature for 30 minutes
  2. extractionThe reaction mixture was extracted with diethyl ether
  3. washThe organic layer was washed with saturated brine
  4. dry with materialdried over anhydrous sodium sulfate
  5. filtrationAfter filtration
  6. customthe solvent was evaporated under reduced pressure
  7. concentrationThe filtrate was concentrated
  8. customdried
  9. dissolutionThe resulting residue was dissolved in dichloroethane (5 ml)
  10. additionTriisopropylsilane (2.27 ml) and boron trifluoride-diethyl ether complex (0.85 ml) were added to the solution at −30° C
  11. stirringAfter stirring at the same temperature for 30 minutes
  12. additionsaturated aqueous solution of sodium bicarbonate was added to the reaction mixture
  13. extractionThe mixture was extracted with diethyl ether
  14. washThe organic layer was washed with saturated brine
  15. dry with materialdried over anhydrous sodium sulfate
  16. filtrationAfter filtration
  17. customthe solvent was evaporated under reduced pressure
  18. customThe resulting residue was purified by silica gel column chromatography (ethyl acetate-n-hexane)

Sources & evidence

ORD record
ord-42289a5cf44847cfaf2b59d6b0c6a876
Source dataset
uspto-grants-2007_01
Patent number
US07169761B2

Reaction notes

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