Cesium carbonate → HCID 58786118, compound

HRID 1376004Notes

Reaction equation

HRID 1376004 reaction equation
C1(P(C2CCCCC2)C2C=[CH:12][CH:11]=[CH:10][C:9]=2[C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)CCCCC1.[F-].[K+].[C:28](=[O:31])([O-])[O-:29].[Cs+].[Cs+].C([O:37][C@@H:38]1[C@@H:43]([O:44]C(=O)C)[C@H:42]([O:48]C(=O)C)[C@@H:41]([CH2:52][O:53]C(=O)C)[O:40][C@H:39]1[C:57]1[CH:62]=[CH:61][CH:60]=[C:59]([CH2:63]Br)[C:58]=1[F:65])(=O)C.O1CCOC[CH2:67]1>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[F:65][C:58]1[C:57]([C@H:39]2[C@H:38]([OH:37])[C@@H:43]([OH:44])[C@H:42]([OH:48])[C@@H:41]([CH2:52][OH:53])[O:40]2)=[CH:62][CH:61]=[CH:60][C:59]=1[CH2:63][C:9]1[CH:10]=[C:11]2[C:19](=[CH:18][CH:17]=[CH:16][CH:15]=[CH:12]2)[C:14]=1[C:28]([O:29][CH3:67])=[O:31]

Participants

7

Reactant 5

HCID 10796Cesium carbonateHCID 312751,4-DioxaneHCID 522689Potassium FluorideHCID 27342162-(Dicyclohexylphosphino)biphenylHCID 58786191HCID 58786191, compound

Product 1

HCID 58786118HCID 58786118, compound

Reagents, catalysts & solvents 1

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Conditions

Temperature
90 °C

Procedure

Tris(dibenzylideneacetone)dipalladium(0) (17 mg), 2-(dicyclohexylphosphino)biphenyl (22 mg), potassium fluoride (44 mg), and cesium carbonate (247 mg) were added to a solution of (1S)-2,3,4,6-tetra-O-acetyl-1,5-anhydro-1-[3-(bromomethyl) -2-fluorophenyl]-D-glucitol (198 mg) and methyl 2-(tributylstanyl)azulene-1-carboxylate (180 mg) in 1,4-dioxane (10 ml) and the mixture was vigorously stirred at 90° C. for 15 hours. The reaction mixture was filtered through celite and the filtrate was concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (ethyl acetate-n-hexane). The resulting residue (71 ml) was dissolved in THF-methanol (ratio: 1:1, 6.0 ml). Sodium methoxide (30 mg) was added to the solution and the resulting mixture was stirred at room temperature overnight. The solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (chloroform-methanol) to obtain methyl 2-[2-fluoro-3-[(2S, 3R,4R,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)tetrahydro-2H-pyran-2-yl]benzyl]azulene-1-carboxylate (19 mg).

Workup

  1. filtrationThe reaction mixture was filtered through celite
  2. concentrationthe filtrate was concentrated under reduced pressure
  3. customThe resulting residue was purified by silica gel column chromatography (ethyl acetate-n-hexane)
  4. dissolutionThe resulting residue (71 ml) was dissolved in THF-methanol (ratio: 1:1, 6.0 ml)
  5. additionSodium methoxide (30 mg) was added to the solution
  6. stirringthe resulting mixture was stirred at room temperature overnight
  7. customThe solvent was evaporated under reduced pressure
  8. customThe residue was purified by silica gel column chromatography (chloroform-methanol)

Sources & evidence

ORD record
ord-07a8f5aaa183425bad94e69ee2e60135
Source dataset
uspto-grants-2007_01
Patent number
US07169761B2

Reaction notes

Loading…