Dimethylformamide → HCID 59504447, compound

HRID 418906Notes

Reaction equation

HRID 418906 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[CH2:11][CH2:10][CH2:9][CH2:8][C:7]=1O)=[O:5])[CH3:2].[CH3:13][O:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=1B(O)O.CN(C=O)C.C(=O)([O-])[O-].[Na+].[Na+]>O.CC([O-])=O.CC([O-])=O.[Pd+2].C1(P(C2C=CC=CC=2)CCCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(OCC)(=O)C.CO>[CH2:1]([O:3][C:4]([C:6]1[CH2:11][CH2:10][CH2:9][CH2:8][C:7]=1[C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][C:15]=1[O:14][CH3:13])=[O:5])[CH3:2]

Participants

10

Reactant 4

HCID 6228DimethylformamideHCID 10340Sodium CarbonateHCID 27339582-Methoxyphenylboronic acidHCID 54695815Ethyl 2-hydroxycyclohex-1-ene-1-carboxylate

Product 1

HCID 59504447HCID 59504447, compoundYield 52%

Reagents, catalysts & solvents 5

HCID 821241,4-Bis(diphenylphosphino)butaneCatalystHCID 167845palladium(II) acetateCatalystHCID 887MethanolSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
70 °C

Procedure

Combine 2-hydroxy-cyclohex-1-enecarboxylic acid ethyl ester (8.92 g, 29.5 mmol), 2-methoxyphenylboronic acid (5.0 g, 32.4 mmol), DMF (60.0 mL), methanol (20.0 mL), and sodium carbonate in water (40.0 g in 40 mL) at room temperature. Purge several times with nitrogen then add Pd(OAc)2 (72.0 mg, 1 mmol %) and 1,4-bis(diphenyl phosphino)butane (170.0 mg) and purge again with nitrogen. Stir at 70° C. under nitrogen for 5 hours then filter reaction wash with Methanol and ethyl acetate. Concentrate reaction mixture on rotovap and add ethyl acetate. Wash 5 times with brine and dry over anhydrous sodium sulfate. Concentrate and flash chromatograph using 5 to 40% ethyl acetate/hexanes eluent to yield the titled compound (3.98 g, 52%). TLC Rf=0.25 in 10% ethyl acetate/hexanes. 1H NMR (CDCl3): 7.2 (t, 1H, J=6.0 Hz), 6.9 (m, 3H),), 3.8 (m, 5H), 2.5 (m, 4H), 1.8 (m, 4H), 0.8 (t, 3H, J=7 Hz).

Workup

  1. customat room temperature
  2. customPurge several times with nitrogen
  3. filtrationthen filter
  4. customreaction
  5. washwash with Methanol and ethyl acetate
  6. concentrationConcentrate
  7. customreaction mixture on rotovap
  8. washWash 5 times with brine
  9. dry with materialdry over anhydrous sodium sulfate
  10. concentrationConcentrate

Sources & evidence

ORD record
ord-7a098624b24b46a4ab473d98795a367a
Source dataset
uspto-grants-2012_01
Patent number
US08093302B2

Reaction notes

Loading…