Cesium carbonate → HCID 89483966, compound

HRID 589253Notes

Reaction equation

HRID 589253 reaction equation
[C:1]([C:5]1[S:9][C:8]([C:10]2[S:11][C:12](/[C:15](/[O:18][C:19]3[CH:24]=[CH:23][CH:22]=[C:21]([O:25][CH3:26])[CH:20]=3)=[CH:16]/Cl)=[CH:13][CH:14]=2)=[CH:7][CH:6]=1)([CH3:4])([CH3:3])[CH3:2].C1C=CC(P(C2C(OC3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=CC=3)=CC=CC=2)C2C=CC=CC=2)=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+].[F-].[Cs+]>O1CCOCC1.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]>[C:1]([C:5]1[S:9][C:8]([C:10]2[S:11][C:12]([C:15]3[O:18][C:19]4[CH:20]=[C:21]([O:25][CH3:26])[CH:22]=[CH:23][C:24]=4[CH:16]=3)=[CH:13][CH:14]=2)=[CH:7][CH:6]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 25953Cesium fluorideHCID 4285986Bis[2-(diphenylphosphino)phenyl] etherHCID 89479861HCID 89479861, compound

Product 1

HCID 89483966HCID 89483966, compound

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent

Procedure

(Z)-5-(tert-butyl)-5′-(2-chloro-1-(3-methoxyphenoxy)vinyl)-2,2′-bithiophene (2.9 g, 7.16 mmol) and DPEphos (0.19 g, 0.36 mmol) were dissolved in anhydrous 1,4-dioxane (40 mL). Cesium carbonate (7.0 g, 21.5 mmol) and cesium fluoride (3.3 g, 21.5 mmol) were added and the reaction mixture was deoxygenated by bubbling argon through it for 1 hour. Tris(dibenzylideneacetone)dipalladium(0) (0.16 g, 0.18 mmol) was added and the reaction mixture was heated to reflux for 20 hours. After cooling to room temperature, the reaction mixture was filtered, poured into water (250 mL), mixed well and separated. The aqueous portion was extracted with ether (2×200 mL) and the combined organics were washed with water (500 mL), dried over MgSO4, filtered and solvent removed by rotary evaporation. The resulting brown solid was redissolved in DCM (250 mL) and deposited onto silica gel. Flash chromatography (combi-flash, hexanes) afforded a yellow, powdery solid, 1.53 g (58%). 1H NMR (600 MHz, CDCl3) δ 7.40 (d, J=8.5 Hz, 1H), 7.29 (d, J=3.8 Hz, 1H), 7.07 (d, J=3.8 Hz, 1H), 7.04 (d, J=1.4 Hz, 1H), 7.01 (d, J=3.6 Hz, 1H), 6.86 (dd, J=8.5, 2.2 Hz, 1H), 6.76 (s, 1H), 6.75 (d, J=3.6 Hz, 1H), 3.87 (s, 3H), 1.41 (s, 9H).

Workup

  1. customthe reaction mixture was deoxygenated
  2. customby bubbling argon through it for 1 hour
  3. temperaturethe reaction mixture was heated
  4. temperatureto reflux for 20 hours
  5. filtrationthe reaction mixture was filtered
  6. additionpoured into water (250 mL)
  7. additionmixed well
  8. customseparated
  9. extractionThe aqueous portion was extracted with ether (2×200 mL)
  10. washthe combined organics were washed with water (500 mL)
  11. dry with materialdried over MgSO4
  12. filtrationfiltered
  13. customsolvent removed by rotary evaporation
  14. dissolutionThe resulting brown solid was redissolved in DCM (250 mL)
  15. customFlash chromatography (combi-flash, hexanes) afforded a yellow, powdery solid, 1.53 g (58%)

Sources & evidence

ORD record
ord-4c66b245fbe746e28dd5998fb691392f
Source dataset
uspto-grants-2016_01
Patent number
US09227986B2

Reaction notes

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