Triethylamine → HCID 12991003, compound

HRID 990746Notes

Reaction equation

HRID 990746 reaction equation
[CH:1]1([C:6]([C:8]2[C:13]([O:14][CH3:15])=[CH:12][CH:11]=[CH:10][C:9]=2OS(C(F)(F)F)(=O)=O)=[O:7])[CH2:5][CH:4]=[CH:3][CH2:2]1.C(N(CC)CC)C.C([O-])(=O)C.[K+].C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CN(C=O)C.[Cl-].[Na+].O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:15][O:14][C:13]1[C:8]2[C:6](=[O:7])[CH:1]3[CH2:5][CH:4]([CH:3]=[CH:2]3)[C:9]=2[CH:10]=[CH:11][CH:12]=1

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 812191,3-Bis(diphenylphosphino)propaneHCID 517044Potassium AcetateHCID 12991002HCID 12991002, compound

Product 1

HCID 12991003HCID 12991003, compoundYield 47%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolventHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
130 °C

Procedure

Trifluoro-methanesulfonic acid 2-(cyclopent-3-enecarbonyl)-3-methoxy-phenyl ester (45.0 g, 129 mmol) was dissolved in DMF (100 mL) under a N2 atmosphere and treated with triethylamine (19.5 g, 193 mmol), potassium acetate (1.89 g, 19.0 mmol) and 1,3-bis(diphenylphosphino)propane (5.30 g, 12.9 mmol). This mixture was stirred and degassed (3 vacuum/N2 purge cycles) then treated wlth palladium acetate (1.16 g, 5.14 mmol). After 20 min. the mixture was warmed to 130° C. for 1 hour, cooled and poured into brine (300 mL). The resulting mixture was extracted with EtOAc (4×100 mL) and the combined organic layer was washed with sat. aq. NaHCO3 soln. (100 mL), H2O (100 mL), and brine (100 mL), dried (MgSO4), filtered and evaporated to an oil. (55 g). The oil was chromatographed on silica gel to provide product as a white solid (12.0 g, 47%). (TLC 25%EtOAc/hexanes Rf 0.27). 1H NMR (CDCl3) δ7.29 (t, J=8.0 Hz, 1H), 6.84 (d, J=8.0 Hz, 1H), 6.73 (d, J=8.0 Hz, 1H), 6.63 (dd, J=5.0,3.0 Hz, 1H), 6.15 (dd, J=5.0,3.0 Hz, 1H), 3.87 (s, 3H), 3.60 (br s, 1H), 3.39 (br s, 1H), 2.56 (AB m, 2H). 13C NMR 195.38, 161.61, 149.82, 143.47, 133.77, 131.84, 131.80, 117.51, 111.46, 57.63, 55.96, 47.63, 47.51. GSMS m/e 200 (M+). mp 135-136° C.

Workup

  1. customdegassed
  2. custom(3 vacuum/N2 purge cycles)
  3. temperaturecooled
  4. extractionThe resulting mixture was extracted with EtOAc (4×100 mL)
  5. washthe combined organic layer was washed with sat. aq. NaHCO3 soln
  6. dry with material(100 mL), H2O (100 mL), and brine (100 mL), dried (MgSO4)
  7. filtrationfiltered
  8. customevaporated to an oil
  9. customThe oil was chromatographed on silica gel

Sources & evidence

ORD record
ord-d04d7d1382414f8fbcc276908ac68304
Source dataset
uspto-grants-2002_10
Patent number
US06462035B1

Reaction notes

Loading…