Triethylamine → HCID 18415739, compound

HRID 990754Notes

Reaction equation

HRID 990754 reaction equation
[CH:1]1([CH2:6][C:7]2[CH:12]=[CH:11][C:10]([O:13][CH3:14])=[CH:9][C:8]=2OS(C(F)(F)F)(=O)=O)[CH2:5][CH:4]=[CH:3][CH2:2]1.C(N(CC)CC)C.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>[CH3:14][O:13][C:10]1[CH:11]=[CH:12][C:7]2[CH2:6][CH:1]3[CH2:5][CH:4]([CH:3]=[CH:2]3)[C:8]=2[CH:9]=1

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 812191,3-Bis(diphenylphosphino)propaneHCID 53711462HCID 53711462, compound

Product 1

HCID 18415739HCID 18415739, compoundYield 95%

Reagents, catalysts & solvents 3

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

Conditions

Temperature
100 °C

Procedure

Trifluoro-methanesulfonic acid 2-cyclopent-3-enylmethyl-5-methoxy-phenyl ester (2.00 g, 5.95 mmol) was dissolved in DMF (10 mL) under a N2 atmosphere and treated with triethylamine (0.91 g, 8.92 mmol) and 1,3-bis(diphenylphosphino)propane (0.37 g, 0.89 mmol). This mixture was stirred and degassed (3 vacuum/N2 purge cycles), and then treated with palladium acetate (93 mg, 0.42 mmol). After stirring for 20 min. the mixture was warmed to 100° C. for 18 hours, cooled and poured into brine (30 mL). The resulting mixture was extracted with EtOAc (4×10 mL) and the combined organic layer was washed with sat. aq. NaHCO3 soln. (10 mL), H2O (10 mL), brine (10 mL), dried (MgSO4), filtered and evaporated to an oil. The oil was chromatographed on Silica gel (2%CH2Cl2/hexanes) to provide product as an oil (1.05 g, 95%). (TLC 10%EtOAc/hexanes Rf 0.52). 1H NMR (CDCl3) δ6.94 (d, J=8.0 Hz, 1H), 6.68 (dd, J=8.0,2.8 Hz, 1H), 6.59 (d, J=2.8 Hz, 1H), 6.23 (dd, J=5.5,2.8 Hz,1H), 5.79 (dd, J=5.5,2.6 Hz, 1H), 3.77 (s, 3H), 3.28 (m, 1H), 2.96-2,89 (m, 2H), 2.49 (d, J=15.5 Hz, 1H), 2.19 (m, 1H), 1.85 (d, J=10.5 Hz, 1H). 13C NMR (CDCl3) 156.94, 144.07, 138.95, 131.24, 131.21, 126.34, 111.73, 111.45, 55.22, 45.10, 40.18, 38.47, 29.49. GCMS m/e 186 (M+).

Workup

  1. customdegassed
  2. custom(3 vacuum/N2 purge cycles)
  3. stirringAfter stirring for 20 min. the mixture
  4. temperaturecooled
  5. extractionThe resulting mixture was extracted with EtOAc (4×10 mL)
  6. washthe combined organic layer was washed with sat. aq. NaHCO3 soln
  7. dry with material(10 mL), H2O (10 mL), brine (10 mL), dried (MgSO4)
  8. filtrationfiltered
  9. customevaporated to an oil
  10. customThe oil was chromatographed on Silica gel (2%CH2Cl2/hexanes)

Sources & evidence

ORD record
ord-bedd5c9d167749f3961f8a79a96e8e40
Source dataset
uspto-grants-2002_10
Patent number
US06462035B1

Reaction notes

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