Sodium Carbonate → HCID 70855260, compound

HRID 591073Notes

Reaction equation

HRID 591073 reaction equation
Br[C:2]1[C:3]([CH:9]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])[C:10]([O:12][CH2:13][CH3:14])=[O:11])=[C:4]([CH3:8])[S:5][C:6]=1[Cl:7].CC1(C)C(C)(C)OB([C:28]2[CH:29]=[C:30]3[C:35](=[CH:36][CH:37]=2)[O:34][CH2:33][CH2:32][CH2:31]3)O1.C(=O)([O-])[O-].[Na+].[Na+]>O1CCOCC1.O.C1(C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)[Pd][P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[C:16]([O:15][CH:9]([C:3]1[C:2]([C:28]2[CH:37]=[CH:36][C:35]3[O:34][CH2:33][CH2:32][CH2:31][C:30]=3[CH:29]=2)=[C:6]([Cl:7])[S:5][C:4]=1[CH3:8])[C:10]([O:12][CH2:13][CH3:14])=[O:11])([CH3:19])([CH3:18])[CH3:17]

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 438110342-(3,4-dihydro-2H-1-benzopyran-6-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 70818559HCID 70818559, compound

Product 1

HCID 70855260HCID 70855260, compoundYield 54.1%

Reagents, catalysts & solvents 3

HCID 178419050HCID 178419050, compoundCatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
85 °C

Procedure

Under argon atmosphere, ethyl 2-(4-bromo-5-chloro-2-methylthiophen-3-yl)-2-(tert-butoxy)acetate (44d) (500 mg, 1.35 mmol), 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)chroman (351.8 mg, 1.35 mmol), sodium carbonate (429 mg, 4.05 mmol) were dissolved in dioxane (28 mL) and water (4 mL). The solution was degassed under argon for 10 minutes and bis(triphenylphosphine)palladium (II) dichloride (142 mg, 0.20 mmol) was added. The reaction was heated and shaken at 85° C. for 8 hours. After cooling at room temperature, the mixture was filtered through celite, rinsed with methanol. The filtrate was concentrated in vacuo and partitioned between ethyl acetate and water. The organic layer was washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was purified by flash chromatography on silica gel (cyclohexane/ethyl acetate 97/3) to give the desired product (44e) (308 mg, 0.73 mmol, 54%).

Workup

  1. customThe solution was degassed under argon for 10 minutes
  2. temperatureThe reaction was heated
  3. temperatureAfter cooling at room temperature
  4. filtrationthe mixture was filtered through celite
  5. washrinsed with methanol
  6. concentrationThe filtrate was concentrated in vacuo
  7. custompartitioned between ethyl acetate and water
  8. washThe organic layer was washed with brine
  9. dry with materialdried over sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated under reduced pressure
  12. customThe crude material was purified by flash chromatography on silica gel (cyclohexane/ethyl acetate 97/3)

Sources & evidence

ORD record
ord-be4cd61bc4b248cdabc70338f3c5fbc0
Source dataset
uspto-grants-2016_01
Patent number
US09238026B2

Reaction notes

Loading…