Cesium fluoride → HCID 58790382, compound

HRID 418720Notes

Reaction equation

HRID 418720 reaction equation
Br[C:2]1[S:10][C:9]2[C:4](=[N:5][CH:6]=[CH:7][C:8]=2[O:11][C:12]2[CH:17]=[CH:16][C:15]([N+:18]([O-:20])=[O:19])=[CH:14][C:13]=2[F:21])[CH:3]=1.[Cl:22][CH2:23][CH2:24][CH2:25][O:26][C:27]1[CH:28]=[C:29](B2OC(C)(C)C(C)(C)O2)[CH:30]=[CH:31][CH:32]=1.[F-].[Cs+].C(=O)(O)[O-].[Na+]>COCCOC.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Cl:22][CH2:23][CH2:24][CH2:25][O:26][C:27]1[CH:32]=[C:31]([C:2]2[S:10][C:9]3[C:4](=[N:5][CH:6]=[CH:7][C:8]=3[O:11][C:12]3[CH:17]=[CH:16][C:15]([N+:18]([O-:20])=[O:19])=[CH:14][C:13]=3[F:21])[CH:3]=2)[CH:30]=[CH:29][CH:28]=1

Participants

8

Reactant 4

HCID 25953Cesium fluorideHCID 516892Sodium BicarbonateHCID 58790190HCID 58790190, compoundHCID 59424521HCID 59424521, compound

Product 1

HCID 58790382HCID 58790382, compoundYield 78%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent

Procedure

Bromothienopyridine 50 (0.88 g, 2.38 mmol), boronate 363 (1.00 g, 3.40 mmol), and tetrakis(triphenylphosphine)palladium (0.10 g, 0.086 mmol) were dissolved in dry DME (100 mL). Cesium fluoride (1.26 g, 8.3 mmol) and sodium bicarbonate (0.70 g, 8.3 mmol) were dissolved in water (5 ml each) and added to the reaction mixture, which was then heated to reflux for 4 h, cooled, and concentrated. The residue was partitioned between ethyl acetate and water, washed with brine, dried (anhydrous MgSO4), filtered, and concentrated. The residue was purified by flash chromatography (eluent 75% dichloromethane/hexanes) to afford 364 (0.85 g, 78% yield). 1H NMR (400 MHz, CDCl3) δ (ppm): 8.60 (d, J=6.3, 1H); 8.27-8.24 (m, 2H); 8.18 (s, 1H); 7.58-7.54 (m, 1H); 7.45-7.36 (m, 2H); 7.31 (t, J=2.0, 1H); 7.07-7.04 (m, 1H); 6.78 (d, J=6.1, 1H); 4.21 (t, J=5.9, 2H); 3.79 (t, J=6.3, 2H); 2.29 (quint, J=6.1, 2H). LRMS (M+H): 459.1.

Workup

  1. additionadded to the reaction mixture, which
  2. temperaturewas then heated
  3. temperatureto reflux for 4 h
  4. temperaturecooled
  5. concentrationconcentrated
  6. customThe residue was partitioned between ethyl acetate and water
  7. washwashed with brine
  8. dry with materialdried (anhydrous MgSO4)
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe residue was purified by flash chromatography (eluent 75% dichloromethane/hexanes)

Sources & evidence

ORD record
ord-0a617214dd5c415590895d4a89832f42
Source dataset
uspto-grants-2012_01
Patent number
US08093264B2

Reaction notes

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