Cesium fluoride → HCID 11105918, compound

HRID 2043319Notes

Reaction equation

HRID 2043319 reaction equation
Br[CH:2]=[C:3]1[O:7][C:6](=[O:8])[CH:5]=[CH:4]1.[S:9]1[CH:13]=[CH:12][CH:11]=[C:10]1B(O)O.[F-].[Cs+]>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.C1(C)C=CC=CC=1.O.[Cl-].[Na+].O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[S:9]1[CH:13]=[CH:12][CH:11]=[C:10]1/[CH:2]=[C:3]1/[CH:4]=[CH:5][C:6](=[O:8])[O:7]/1

Participants

9

Reactant 3

HCID 25953Cesium fluorideHCID 27339602-Thiopheneboronic acidHCID 672283605-(Bromomethylidene)furan-2(5H)-one

Product 1

HCID 11105918HCID 11105918, compound

Reagents, catalysts & solvents 5

HCID 67553Tetrabutylammonium IodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

A mixture containing 5-bromomethylene-2(5H)furanone (0.175 g, 1 mmol), 2-thiopheneboronic acid (0.154 g, 1.2 mmol), trans-dichlorobis(triphenylphosphine)palladium (II) (0.035 g, 0.05 mmol), tetrabutylammonium iodide (0.018 g, 0.05 mmol) and cesium fluoride (0.456 g, 3 mmol) in toluene (10 mL) and water (10 mL) were stirred at reflux for 24 hours under nitrogen. After cooling, brine (50 mL) was added and the product extracted with ethyl acetate (50 mL×3). The organic fractions were combined, washed with brine (50 mL×3), dried over anhydrous sodium sulfate and evaporated to dryness to give a brown solid. The resulting solid was chromatographed (silica gel: eluent 50:50 dichloromethane/light petroleum) giving the desired product 32 as a yellow powder. Yield 0.170 g (95%), m.p. 100-102° C. 1H NMR (CDCl3) δ 7.50 (d, J=4.9 Hz, 1H, H3′), 7.46 (d, J=5.3 Hz, 1H, H4), 7.38 (d, J=3.4 Hz, 1H, H5′), 7.08-7.05 (m, 1H, H4′), 6.31 (s, 1H, H6), 6.17 (d, J=5.3 Hz, 1H, H3). 13C NMR (CDCl3, 75 MHz) δ 169.5 (C), 146.6 (C), 143.8 (CH), 136.0 (C), 131.3 (CH), 130.7 (CH), 127.7 (CH), 118.0 (CH), 107.5 (CH). IR (Nujol) 1777, 1738, 1459, 1417, 1376, 1107, 935, 886, 731 cm−1.

Workup

  1. temperatureat reflux for 24 hours under nitrogen
  2. temperatureAfter cooling
  3. extractionthe product extracted with ethyl acetate (50 mL×3)
  4. washwashed with brine (50 mL×3)
  5. dry with materialdried over anhydrous sodium sulfate
  6. customevaporated to dryness
  7. customto give a brown solid
  8. customThe resulting solid was chromatographed (silica gel: eluent 50:50 dichloromethane/light petroleum)

Sources & evidence

ORD record
ord-5eacf4f945744735a5011a4c9882a875
Source dataset
uspto-grants-2013_11
Patent number
US08586618B2

Reaction notes

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