Sodium Bicarbonate → tert-butyl 4-(adamantan-1-ylmethoxy)-2-fluoro-5-((E)-3-methoxyprop-1-en-1-yl)benzoate

HRID 1849759Notes

Reaction equation

HRID 1849759 reaction equation
[C:1]12([CH2:11][O:12][C:13]3[C:25](Br)=[CH:24][C:16]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])=[C:15]([F:27])[CH:14]=3)[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH2:2]1)[CH2:8]2.[CH3:28][O:29][CH2:30]/[CH:31]=[CH:32]/B(O)O.C(=O)(O)[O-].[Na+]>O1CCOCC1.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:1]12([CH2:11][O:12][C:13]3[C:25](/[CH:32]=[CH:31]/[CH2:30][O:29][CH3:28])=[CH:24][C:16]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])=[C:15]([F:27])[CH:14]=3)[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH2:2]1)[CH2:8]2

Participants

6

Reactant 3

HCID 516892Sodium BicarbonateHCID 6274701[(E)-3-methoxyprop-1-enyl]boronic acidHCID 86703641Tert-butyl 4-(adamantan-1-ylmethoxy)-5-bromo-2-fluorobenzoate

Product 1

HCID 86703642tert-butyl 4-(adamantan-1-ylmethoxy)-2-fluoro-5-((E)-3-methoxyprop-1-en-1-yl)benzoate

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
150 °C

Procedure

To a mixture of tert-butyl 4-(adamantan-1-ylmethoxy)-5-bromo-2-fluorobenzoate (1.00 g, 2.28 mmol) in dioxane (15 mL) was added tetrakis(triphenylphosphine)palladium (0.263 g, 0.23 mmol), (E)-3-methoxy-1-propen-1-ylboronic acid, pinacol ester (1.36 g, 6.80 mmol), and 2 M sodium bicarbonate solution (4.5 mL, 9.00 mmol). The reaction mixture was thoroughly degassed by passing argon through it and then heated in a microwave at 150° C. for 30 minutes. After cooling to ambient temperature, the mixture was diluted with ethyl acetate (100 mL) and filtered over anhydrous sodium sulfate. Removal of all volatiles under reduced pressure gave a residue which was purified by silica gel column chromatography using 0-50% ethyl acetate in hexanes as eluent to afford tert-butyl 4-(adamantan-1-ylmethoxy)-2-fluoro-5-((E)-3-methoxyprop-1-en-1-yl)benzoate (1.17 g, quant.) as a colorless oil.

Workup

  1. customThe reaction mixture was thoroughly degassed
  2. temperatureAfter cooling to ambient temperature
  3. additionthe mixture was diluted with ethyl acetate (100 mL)
  4. filtrationfiltered over anhydrous sodium sulfate
  5. customRemoval of all volatiles under reduced pressure
  6. customgave a residue which
  7. customwas purified by silica gel column chromatography

Sources & evidence

ORD record
ord-815aaf8d519846ec879eef7ed713f3ae
Source dataset
uspto-grants-2015_02
Patent number
US08952169B2

Reaction notes

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