Triethylamine → 1,1-Dimethylethyl (2E)-3-{4-[bicyclo[3.3.1]non-9-ylidene(4-hydroxyphenyl)methyl]phenyl}-2-propenoate

HRID 1716009Notes

Reaction equation

HRID 1716009 reaction equation
[CH:1]12[C:9](=[C:10]([C:18]3[CH:23]=[CH:22][C:21](Br)=[CH:20][CH:19]=3)[C:11]3[CH:16]=[CH:15][C:14]([OH:17])=[CH:13][CH:12]=3)[CH:5]([CH2:6][CH2:7][CH2:8]1)[CH2:4][CH2:3][CH2:2]2.[C:25]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])(=[O:28])[CH:26]=[CH2:27].CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.CCN(CC)CC>CC([O-])=O.CC([O-])=O.[Pd+2].CC#N>[CH:1]12[C:9](=[C:10]([C:11]3[CH:16]=[CH:15][C:14]([OH:17])=[CH:13][CH:12]=3)[C:18]3[CH:23]=[CH:22][C:21](/[CH:27]=[CH:26]/[C:25]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])=[CH:20][CH:19]=3)[CH:5]([CH2:6][CH2:7][CH2:8]1)[CH2:4][CH2:3][CH2:2]2

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 15458tert-Butyl acrylateHCID 80271Tri-o-tolylphosphineHCID 686546174-[Bicyclo[3.3.1]non-9-ylidene(4-bromophenyl)methyl]phenol

Product 1

HCID 689795521,1-Dimethylethyl (2E)-3-{4-[bicyclo[3.3.1]non-9-ylidene(4-hydroxyphenyl)methyl]phenyl}-2-propenoateYield 92%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
85 °C

Procedure

Compound 43 (0.32 g, 0.834 mmol), t-butyl acrylate (0.734 mL, 5.01 mmol), P(o-tolyl)3 (0.11 g, 0.359 mmol), Pd(OAc)2 (0.0394 g, 0.175 mmol) and Et3N (0.7 mL, 5.01 mmol) were added to a flask containing CH3CN (13 mL) and the stirred reaction mixture was heated at 85° C. for 24 h under a nitrogen atmosphere. The reaction mixture was allowed to cool at RT and then partitioned between water and EtOAc. The layers were separated, and the organic phase was washed with brine, dried (MgSO4), filtered, and the filtrate was concentrated to give an oily residue. The crude oil was adsorbed onto silica and purified by flash column chromatography on silica gel with a hexanes:EtOAc gradient (100:0 to 50:50) to give compound 44 as a yellow foam (0.33 g, 92%). 1H NMR (400 MHz, DMSO-d6): δ 1.45-1.53 (m, 10H), 1.72-1.73 (m, 7H), 1.96-2.01 (m, 2H), 2.53-2.64 (m, 4H), 6.42 (d, J=16.1 Hz, 1H), 6.66 (d, J=8.5 Hz, 2H), 6.87 (d, J=8.3 Hz, 2H), 7.08 (d, J=8.1 Hz, 2H), 7.48 (d, J=16.1 Hz, 1H), 7.57 (d, J=8.1 Hz, 2H), 9.30 (s, 1H).

Workup

  1. customthe stirred reaction mixture
  2. temperatureto cool at RT
  3. custompartitioned between water and EtOAc
  4. customThe layers were separated
  5. washthe organic phase was washed with brine
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationthe filtrate was concentrated
  9. customto give an oily residue
  10. custompurified by flash column chromatography on silica gel with a hexanes

Sources & evidence

ORD record
ord-8a812f4d2ef24bdb8e2b938ee35b9257
Source dataset
uspto-grants-2010_09
Patent number
US07799828B2

Reaction notes

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