Sodium Carbonate → HCID 87972489, compound

HRID 2180558Notes

Reaction equation

HRID 2180558 reaction equation
BrC1C=[C:4]2[C:9](=[CH:10]C=1OCC)[C:8]([CH3:16])([CH3:15])[CH2:7][CH:6]=[C:5]2[C:17]([CH3:20])([CH3:19])[CH3:18].B1(B2O[C:33]([CH3:36])([CH3:35])[C:32]([CH3:38])([CH3:37])O2)OC(C)(C)C(C)(C)O1.[C:39]([O-])(=[O:41])[CH3:40].[K+].C(C1C2C=C(B3OC(C)(C)C(C)(C)O3)C(OCC)=CC=2C(C)(C)CC=1)(C)(C)C.I/C(/C)=C\[CH:75]=[CH:76]\[C:77](\[CH3:84])=[CH:78]\[C:79]([O:81][CH2:82][CH3:83])=[O:80].C(=O)([O-])[O-].[Na+].[Na+]>CN(C)C=O.C1(C)C=CC=CC=1.C(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>[C:17]([C:5]1[C:4]2[CH:37]=[C:32](/[C:33](/[CH3:35])=[CH:36]\[CH:75]=[CH:76]\[C:77](\[CH3:84])=[CH:78]\[C:79]([O:81][CH2:82][CH3:83])=[O:80])[C:38]([O:41][CH2:39][CH3:40])=[CH:10][C:9]=2[C:8]([CH3:15])([CH3:16])[CH2:7][CH:6]=1)([CH3:18])([CH3:19])[CH3:20]

Participants

11

Reactant 6

HCID 10340Sodium CarbonateHCID 517044Potassium AcetateHCID 2733548Bis(pinacolato)diboraneHCID 22490955HCID 22490955, compoundHCID 69729649HCID 69729649, compoundHCID 87972285HCID 87972285, compound

Product 1

HCID 87972489HCID 87972489, compound

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 1140TolueneSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

A solution of 6-bromo-4-tert-butyl-7-ethoxy-1,1-dimethyl-1,2-dihydronaphthalene (Compound A-6, 350 mg, 1.04 mmol), bis(pinacolato)diboron (370 mg, 1.46 mmol), and potassium acetate (305 mg, 3.12 mmol) in dimethylformamide (8 mL) was purged with argon for 15 minutes. [1, 1-bis(disphenylphosphino)ferrocene]dichloropalladium(II) (1:1 complex with dichloromethane, 82 mg, 0.1 mmol) was added and purged with argon for another 5 min. The reaction was continuously stirred at 80° C. for 4 days under argon. Thereafter the reaction was cooled to room temperature and quenched with water. The reaction mixture was extracted with ethyl acetate. The organic layer was washed successively with water, brine, dried over Na2SO4, and concentrated in vacuo. Purification by column chromatography (silica gel, 10 to 20% ethyl acetate in hexane) yielded a mixture of 2-(8-tert-butyl-3-ethoxy-5,5-dimethyl-5,6-dihydronaphthalen-2-yl)-4,4,5,5-tetramethyl [1,3,2]dioxaborolane (Compound A-8) and 2-(8-tert-butyl-1-(3-ethoxy-5,5-dimethyl-5,6-dihydro-naphthalen-2-yl)boronic acid (Compound A-10). The above mixture of Compounds A-8 and A-10, ethyl 7-iodo-3-methyl-octa-2E,4E,6Z-trienoate (Compound A-11, 130 mg, 0.43 mmol), tetrakis(triphenylphosphine)palladium(0) (40 mg, 0.03 mmol), and 2M sodium carbonate (1 mL, 2 mmol) in toluene (4 mL) and ethanol (2 mL) was heated to 100° C. for 40 h. The reaction was cooled to room temperature and extracted with ethyl acetate. The organic layer was washed with brine, dried over Na2SO4, and concentrated in vacuo. Purification by column chromatography (silica gel 1% to 2% ethyl acetate in hexane) yielded the title compound as an oil.

Workup

  1. custompurged with argon for another 5 min
  2. temperatureThereafter the reaction was cooled to room temperature
  3. customquenched with water
  4. extractionThe reaction mixture was extracted with ethyl acetate
  5. washThe organic layer was washed successively with water, brine
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated in vacuo
  8. customPurification by column chromatography (silica gel, 10 to 20% ethyl acetate in hexane)
  9. customyielded
  10. additionThe above mixture of Compounds
  11. temperatureThe reaction was cooled to room temperature
  12. extractionextracted with ethyl acetate
  13. washThe organic layer was washed with brine
  14. dry with materialdried over Na2SO4
  15. concentrationconcentrated in vacuo
  16. customPurification by column chromatography (silica gel 1% to 2% ethyl acetate in hexane)

Sources & evidence

ORD record
ord-84eed7b1426d4a83ae3f5c449d29a6d9
Source dataset
uspto-grants-2005_05
Patent number
US06887896B1

Reaction notes

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