Diisopropylethylamine → 5,6-Difluorotricyclo[7.2.1.02,7]dodeca-2(7),3,5,10-tetraene

HRID 49157Notes

Reaction equation

HRID 49157 reaction equation
[CH:1]1([CH2:6][C:7]2[C:12]([F:13])=[C:11]([F:14])[CH:10]=[CH:9][C:8]=2OS(C(F)(F)F)(=O)=O)[CH2:5][CH:4]=[CH:3][CH2:2]1.C(N(C(C)C)CC)(C)C.C([O-])(=O)C.[K+]>CN(C=O)C.[Cl-].[Na+].O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>[F:14][C:11]1[CH:10]=[CH:9][C:8]2[CH:4]3[CH2:5][CH:1]([CH2:6][C:7]=2[C:12]=1[F:13])[CH:2]=[CH:3]3

Participants

8

Reactant 3

HCID 81531DiisopropylethylamineHCID 517044Potassium AcetateHCID 12990998HCID 12990998, compound

Product 1

HCID 129723185,6-Difluorotricyclo[7.2.1.02,7]dodeca-2(7),3,5,10-tetraeneYield 60%

Reagents, catalysts & solvents 4

HCID 80271Tri-o-tolylphosphineCatalystHCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolventHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
100 °C

Procedure

Trifluoro-methanesulfonic acid 2-cyclopent-3-enylmethyl-3,4-difluoro-phenyl ester (340 mg, 0.99 mmol), was dissolved In DMF (5 mL) under a N2 atmosphere and treated with diisopropylethylamine (0.26 mL, 1.5 mmol, potassium acetate (981 mg, 10.0 mmol) and tri-o-tolylphosphine (12 mg, 0.04 mmol). This mixture was stirred and degassed (3 vacuum/N2 purge cycles) and then treated with palladium acetate (5 mg, 0.02 mmol). After 20 min. the mixture was warmed to 100° C. for 18 hours, cooled and poured into brine (50 mL). The resulting mixture was extracted with hexanes (4×25 mL) and the combined organic layer was washed with a sat. aq. NaHCO3 soln. (10 mL), water (H2O) (10 mL), brine (10 mL), dried (magnesium sulfate (MgSO4)), filtered and and chromatographed on silica gel to provide an oil (110 mg, 60%). (TLC hexanes Rf 0.58). 1H NMR (CDCl3) δ 6.80 (ddd, J=6.6, 8.1, 8.3 Hz, 1H), 6.68 (m, 1H), 6.17 (dd, J=5.5, 2.8 Hz, 1H), 5.77 (dd, J=5.5, 2.8 Hz, 1H), 3.29 (br s, 1H), 2.96 (br s, 1H), 2.84 (AB dd, J=17.9, 5.0 Hz. 1H), 2.54 (AB d, J=17.9 Hz, 1H), 2.19 (m, 1H), 1.77 (d, J=10.5 Hz, 1H). GCMS m/e 192 (M+).

Workup

  1. customdegassed
  2. custom(3 vacuum/N2 purge cycles)
  3. temperaturecooled
  4. extractionThe resulting mixture was extracted with hexanes (4×25 mL)
  5. washthe combined organic layer was washed with a sat. aq. NaHCO3 soln
  6. dry with material(10 mL), water (H2O) (10 mL), brine (10 mL), dried (magnesium sulfate (MgSO4))
  7. filtrationfiltered
  8. customchromatographed on silica gel

Sources & evidence

ORD record
ord-9e9762313d544c7497990d3d4d20a5a7
Source dataset
uspto-grants-2004_03
Patent number
US06706702B2

Reaction notes

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