Metaperiodic acid → 3-(2,2,3,3-Tetrafluoro-propoxy)-4-trifluoromethylphenylboronic acid

HRID 1755086Notes

Reaction equation

HRID 1755086 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]([F:11])([F:10])[F:9])=[C:4]([O:12][CH2:13][C:14]([F:19])([F:18])[CH:15]([F:17])[F:16])[CH:3]=1.[B:20]1(B2OC(C)(C)C(C)(C)O2)[O:24]C(C)(C)C(C)(C)[O:21]1.C([O-])(=O)C.[K+].I(O)(=O)(=O)=O>COC1CCCC1.[Pd](Cl)Cl.C1(P([C-]2C=CC=C2)C2C=CC=CC=2)C=CC=CC=1.[CH-]1C=CC=C1.[Fe+2].O>[F:18][C:14]([F:19])([CH:15]([F:17])[F:16])[CH2:13][O:12][C:4]1[CH:3]=[C:2]([B:20]([OH:24])[OH:21])[CH:7]=[CH:6][C:5]=1[C:8]([F:11])([F:10])[F:9]

Participants

8

Reactant 4

HCID 65185Metaperiodic acidHCID 517044Potassium AcetateHCID 2733548Bis(pinacolato)diboraneHCID 871667454-Bromo-2-(2,2,3,3-tetrafluoro-propoxy)-1-trifluoromethyl-benzene

Product 1

HCID 871666723-(2,2,3,3-Tetrafluoro-propoxy)-4-trifluoromethylphenylboronic acidYield 60%

Reagents, catalysts & solvents 3

HCID 178479793cyclopenta-1,3-diene;cyclopenta-2,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+)CatalystHCID 962WaterSolvent2×HCID 138539Cyclopentyl methyl etherSolvent

Conditions

Temperature
115 °C

Procedure

A solution of 4-bromo-2-(2,2,3,3-tetrafluoro-propoxy)-1-trifluoromethyl-benzene (482 mg, 1.36 mmol), pinacol diborane (379 mg, 1.49 mmol), palladium dichloride-diphenylphosphinoferrocene (111 mg, 0.136 mmol) and potassium acetate (400 mg, 4.08 mmol) in cyclopentyl methyl ether (2.41 mL) was heated with stirring at 115° C. for one hour in a nitrogen atmosphere. After cooling to room temperature, water (1 mL) was added to the reaction mixture, and the upper cyclopentyl methyl ether layer was extracted. Methanol (1 mL) was added to the organic layer. Periodic acid (1.24 g, 5.44 mmol) was added at 0° C., and the mixture was warmed to room temperature and stirred for one hour. Water was added to the reaction mixture, followed by extraction with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane:ethyl acetate=3:1→1:1) and further treated with hexane to give 3-(2,2,3,3-tetrafluoro-propoxy)-4-trifluoromethylphenylboronic acid as a pale brown solid (260 mg, 60%).

Workup

  1. temperatureAfter cooling to room temperature
  2. extractionthe upper cyclopentyl methyl ether layer was extracted
  3. additionMethanol (1 mL) was added to the organic layer
  4. temperaturethe mixture was warmed to room temperature
  5. stirringstirred for one hour
  6. extractionfollowed by extraction with ethyl acetate
  7. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was purified by silica gel column chromatography (hexane:ethyl acetate=3:1→1:1)
  10. additionfurther treated with hexane

Sources & evidence

ORD record
ord-213ee76f12154e9eb16ef87c935be55e
Source dataset
uspto-grants-2015_10
Patent number
US09169254B2

Reaction notes

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