Potassium Carbonate → HCID 58238626, compound

HRID 1037657Notes

Reaction equation

HRID 1037657 reaction equation
C(=O)([O-])[O-].[K+].[K+].Br[C:8]1[CH:13]=[CH:12][CH:11]=[C:10]([C:14]([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)=[CH2:15])[N:9]=1.B(O)O.B([O-])[O-].O1[CH2:33][CH2:32][O:31][CH2:30][CH2:29]1>O.C(OCC)(=O)C.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.[Pd]>[CH2:30]([O:31][C:32]1[C:33]([C:14]([CH3:16])([CH3:15])[CH3:10])=[CH:11][CH:12]=[CH:13][C:8]=1[C:8]1[CH:13]=[CH:12][CH:11]=[C:10]([C:14]([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)=[CH2:15])[N:9]=1)[C:29]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1

Participants

10

Reactant 5

HCID 11430Potassium CarbonateHCID 312751,4-DioxaneHCID 61668Boronic AcidHCID 58238609HCID 58238609, compoundHCID 178514824HCID 178514824, compound

Product 1

HCID 58238626HCID 58238626, compoundYield 80%

Reagents, catalysts & solvents 4

HCID 23938PalladiumCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

Potassium carbonate (1.6 g, 11.5 mmol, 3.0 equiv) was dissolved in water (15 mL) and added to compound 8A (1.0 g, 3.9 mmol, 1.0 equiv) and boronic acid 11 (2.0 g, 5.4 mmol, 1.4 equiv) in dioxane (30 mL). A stream of nitrogen was bubbled through the solution for 15 min and tetrakis(triphenylphosphine)palladium(0) (0.02 g, 0.02 mmol, 0.005 equiv) was added to the reaction. The reaction was refluxed for 4 hr at which point LC/MS and TLC indicated the reaction not to be complete. More of the boronate (0.7 g, 1.95 mmol, 0.5 equiv) and the palladium reagent (0.02 g) were added and refluxing was continued for 4 hr. The reaction was allowed to cool to room temperature, diluted with ethyl acetate (50 mL) and the organic layer separated and washed with saturated brine (50 mL). The organic layer was dried over sodium sulfate and absorbed onto silica gel (5 g) by concentration under reduced pressure. This material was purified on a silica gel column (45 g) by eluting with heptanes ethyl acetate (1%) in heptanes (300 mL) and ethyl acetate (3%) in heptanes (500 mL). The desired product was isolated in 80% yield (1.0 g).

Workup

  1. customA stream of nitrogen was bubbled through the solution for 15 min
  2. temperatureThe reaction was refluxed for 4 hr at which point LC/MS and TLC
  3. customthe reaction not
  4. temperaturerefluxing
  5. customthe organic layer separated
  6. washwashed with saturated brine (50 mL)
  7. dry with materialThe organic layer was dried over sodium sulfate
  8. customabsorbed onto silica gel (5 g) by concentration under reduced pressure
  9. customThis material was purified on a silica gel column (45 g)
  10. washby eluting with heptanes ethyl acetate (1%) in heptanes (300 mL) and ethyl acetate (3%) in heptanes (500 mL)

Sources & evidence

ORD record
ord-bbeefbe41c5446c6b8bb779a73140148
Source dataset
uspto-grants-2013_10
Patent number
US08546501B2

Reaction notes

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