Trimethyl borate → HCID 22557673, compound

HRID 984416Notes

Reaction equation

HRID 984416 reaction equation
C([Li])(C)(C)C.Br[C:7]1[CH:12]=[CH:11][C:10](/[CH:13]=[CH:14]/[CH2:15][O:16][Si](C(C)(C)C)(C)C)=[CH:9][CH:8]=1.COB(OC)OC.Br[C:32]1[CH:37]=[C:36]([C:38]([CH3:41])([CH3:40])[CH3:39])[CH:35]=[C:34]([C:42]([CH3:45])([CH3:44])[CH3:43])[CH:33]=1.C(=O)([O-])[O-].[Na+].[Na+].[F-].C([N+](CCCC)(CCCC)CCCC)CCC>COCCOC.Cl.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.C1COCC1>[C:42]([C:34]1[CH:33]=[C:32]([C:7]2[CH:8]=[CH:9][C:10](/[CH:13]=[CH:14]/[CH2:15][OH:16])=[CH:11][CH:12]=2)[CH:37]=[C:36]([C:38]([CH3:41])([CH3:40])[CH3:39])[CH:35]=1)([CH3:45])([CH3:44])[CH3:43]

Participants

11

Reactant 6

HCID 8470Trimethyl borateHCID 10340Sodium CarbonateHCID 6201361-Bromo-3,5-di-tert-butylbenzeneHCID 2724141Tetrabutylammonium FluorideHCID 22557710HCID 22557710, compoundHCID 178418306HCID 178418306, compound

Product 1

HCID 22557673HCID 22557673, compoundYield 20%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 313Hydrochloric AcidSolvent2×HCID 8028TetrahydrofuranSolventHCID 80711,2-DimethoxyethaneSolvent2×

Conditions

Temperature
80 °C

Procedure

tert-Butyllithium (1.7M in pentane, 3.5 ml, 6.0 mmol) was added dropwise, at −78° C. to a stirred THF (10 ml) solution of (E)-[3-(4-bromo-phenyl)-allyloxy]-tert-butyldimethylsilane (982 mg, 3.0 mmol) and the resulting solution stirred for 45 min. Trimethylborate (0.51 ml, 4.50 mmol) was added, the solution allowed to warm to room temperature over 2h, and the solvents evaporated to give the crude boronate ester as a yellow gum, which was dissolved in DME (10 ml). Tetrakis(triphenylphosphine)palladium(0) (69 mg, 0.06 mmol), was added to a stirred DME (20 ml) solution of 1-bromo-3,5-di-tert-butylbenzene (538 mg, 2.0 mmol), the solution stirred for 10 min, aqueous sodium carbonate (2M, 9 ml, 18.0 mmol) added, and stirring continued for a further 10 min. The boronate ester solution was added and the mixture heated to 80° C., under reflux, for 24 h. The resulting mixture was diluted with 1N HCl (50 ml), the products extracted into ethyl acetate (3×50 ml), and the combined extracts washed with brine, dried (MgSO4), and evaporated. The resulting yellow gum was dissolved in dry THF (20 ml), tetra-n-butyl ammonium fluoride (1.26 g, 4.0 mmol) added and the solution stirred at room temperature for 18h. The resulting mixture was diluted with 1N HCl (50 ml), and the products extracted into ethyl acetate (2×50 ml). The combined organic phases were washed with brine, dried (MgSO4), and evaporated to give the colourless glass, (E)-3-(3′,5′-di-tert-butyl-biphenyl-4-yl)-prop-2-en-1-ol (127 mg, 20%).

Workup

  1. customthe solvents evaporated
  2. customto give the crude boronate ester as a yellow gum, which
  3. stirringthe solution stirred for 10 min
  4. stirringstirring
  5. waitcontinued for a further 10 min
  6. temperatureunder reflux, for 24 h
  7. extractionthe products extracted into ethyl acetate (3×50 ml)
  8. washthe combined extracts washed with brine
  9. dry with materialdried (MgSO4)
  10. customevaporated
  11. dissolutionThe resulting yellow gum was dissolved in dry THF (20 ml)
  12. stirringthe solution stirred at room temperature for 18h
  13. extractionthe products extracted into ethyl acetate (2×50 ml)
  14. washThe combined organic phases were washed with brine
  15. dry with materialdried (MgSO4)
  16. customevaporated

Sources & evidence

ORD record
ord-e252f419d82944448a42be128bdf6986
Source dataset
uspto-grants-2005_03
Patent number
US06867218B2

Reaction notes

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