Cesium carbonate → HCID 42625981, compound

HRID 2236541Notes

Reaction equation

HRID 2236541 reaction equation
[O:1]1[CH:5]=[CH:4][C:3](B(O)O)=[CH:2]1.[C:9](=[O:12])([O-])[O-].[Cs+].[Cs+].[Br-].[K+].[F-].[CH2:18]([N+](CCCC)(CCCC)CCCC)CCC.[O:35]1[CH2:40][CH2:39][O:38][CH2:37][CH2:36]1>[Cl-].[NH4+].O1CCCC1.O>[OH:35][CH2:36][C:37]1[O:38][CH:39]=[C:40]([C:3]2[CH:4]=[CH:5][O:1][CH:2]=2)[C:9](=[O:12])[CH:18]=1

Participants

9

Reactant 5

HCID 10796Cesium carbonateHCID 312751,4-DioxaneHCID 253877Potassium BromideHCID 2724141Tetrabutylammonium FluorideHCID 2734358Furan-3-boronic acid

Product 1

HCID 42625981HCID 42625981, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 25517Ammonium ChlorideSolvent

Conditions

Temperature
60 °C

Procedure

A mixture of trifluoro-methanesulfonic acid 6-(tert-butyl-dimethyl-silanyloxymethyl)-4-oxo-4H-pyran-3-yl ester1 (6.94 g, 17.8 mmole), furan-3-boronic acid (4.0 g, 35.7 mmole), tetrakistriphenylphosphine palladium (1.024 g, 0.87 mmole), cesium carbonate (16.32 g, 50.1 mmole) and potassium bromide (10.63 g, 89.3 mmole) in (250 mL) dioxane (250 mL) is heated to 60° C. and stirred overnight. The reaction mixture is cooled to room temperature and diluted with saturated aqueous ammonium chloride and extracted with ethyl acetate. The combined ethyl acetate layers were washed with water, dried over sodium sulfate, filtered, diluted with an equal volume of hexanes and passed thru a short column of magnesol and silica gel eluting with 1:1 hexanes/ethyl acetate. The product is eluted with 2:1 ethyl acetate/hexanes, the solvents were evaporated, triturated with 1:1 hexanes/ethyl acetate, filtered, washed with the same solvent and air dried to give an off white solid, 2.58 g; MS (ES+): m/z 307.3(M+H). This solid is dissolved in tetrahydrofuran and tetrabutylammonium fluoride solution in tetrahydrofuran (40.0 mL, 40.0 mmole) is added and the mixture stirred at room temperature overnight. The reaction mixture is diluted with water and extracted with ethyl acetate. The combined ethyl acetate layers were combined and washed with water, dried over sodium sulfate, filtered, diluted with an equal volume of hexanes and passed thru a short column of magnesol and silica gel eluting with 1:1 hexanes/ethyl acetate. The product is eluted with 2:1 ethyl acetate/hexanes, the solvents were evaporated, triturated with 1:1 hexanes/ethyl acetate, filtered, washed with the same solvent and air dried to give an off white solid, 2.06 g, (37%); MS (ES+): m/z 193.2(M+H). (T. Kamino, et. al.; Tet. Lett. 44 (2003) 7349)

Workup

  1. temperatureThe reaction mixture is cooled to room temperature
  2. extractionextracted with ethyl acetate
  3. washThe combined ethyl acetate layers were washed with water
  4. dry with materialdried over sodium sulfate
  5. filtrationfiltered
  6. additiondiluted with an equal volume of hexanes
  7. washThe product is eluted with 2:1 ethyl acetate/hexanes
  8. customthe solvents were evaporated
  9. customtriturated with 1:1 hexanes/ethyl acetate
  10. filtrationfiltered
  11. washwashed with the same solvent and air
  12. customdried
  13. customto give an off white solid, 2.58 g
  14. stirringthe mixture stirred at room temperature overnight
  15. extractionextracted with ethyl acetate
  16. washwashed with water
  17. dry with materialdried over sodium sulfate
  18. filtrationfiltered
  19. additiondiluted with an equal volume of hexanes
  20. washThe product is eluted with 2:1 ethyl acetate/hexanes
  21. customthe solvents were evaporated
  22. customtriturated with 1:1 hexanes/ethyl acetate
  23. filtrationfiltered
  24. washwashed with the same solvent and air
  25. customdried
  26. customto give an off white solid, 2.06 g, (37%)

Sources & evidence

ORD record
ord-13057a6d01504a65bc090f3083ad2a01
Source dataset
uspto-grants-2010_05
Patent number
US07713994B2

Reaction notes

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