Triethylamine → 1,1-Dimethylethyl (2E)-3-{4-[cyclopentylidene(4-hydroxyphenyl)methyl]phenyl}-2-propenoate

HRID 1715982Notes

Reaction equation

HRID 1715982 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8](=[C:16]2[CH2:20][CH2:19][CH2:18][CH2:17]2)[C:9]2[CH:14]=[CH:13][C:12]([OH:15])=[CH:11][CH:10]=2)=[CH:4][CH:3]=1.[C:21]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])(=[O:24])[CH:22]=[CH2:23].CCN(CC)CC.CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>CC([O-])=O.CC([O-])=O.[Pd+2].O.CCOC(C)=O.CC#N>[C:16]1(=[C:8]([C:9]2[CH:14]=[CH:13][C:12]([OH:15])=[CH:11][CH:10]=2)[C:5]2[CH:6]=[CH:7][C:2](/[CH:23]=[CH:22]/[C:21]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])=[CH:3][CH:4]=2)[CH2:20][CH2:19][CH2:18][CH2:17]1

Participants

9

Reactant 4

HCID 8471TriethylamineHCID 15458tert-Butyl acrylateHCID 80271Tri-o-tolylphosphineHCID 686545024-[(4-Bromophenyl)(cyclopentylidene)methyl]phenol

Product 1

HCID 689778841,1-Dimethylethyl (2E)-3-{4-[cyclopentylidene(4-hydroxyphenyl)methyl]phenyl}-2-propenoateYield 74.5%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
85 °C

Procedure

4-[(4-Bromophenyl)(cyclopentylidene)methyl]phenol (3) (0.351 g, 1.07 mmol), tert-butyl acrylate (0.94 mL, 0.82 g, 6.4 mmol, 6 eq), Pd(OAc)2 (0.051 g, 0.23 mmol, 0.21 eq), Et3N (0.89 mL, 0.65 g, 6.4 mmol, 6 eq), P(o-tolyl)3 (0.139 g, 0.46 mmol, 0.43 eq), and anhydrous CH3CN (16 mL) were combined in a round-bottomed flask and the reaction mixture was heated overnight at 85° C., with stirring, under a nitrogen atmosphere. The reaction mixture was allowed to cool to room temperature and transferred to a separatory funnel with the aid of EtOAc and water. The layers were separated and the organic phase was washed with brine, dried over MgSO4, filtered, and the filtrate was concentrated to give the crude product. The crude product was purified by flash chromatography on silica gel with hexanes:EtOAc (100:0 to 50:50) to give 0.30 g (74%) of compound 4 as a pale yellow solid. 1H NMR (400 MHz, DMSO-d6) δ 1.45 (s, 9H), 1.60 (m, 4H), 2.30 (m, 4H), 6.43 (d, J=15.9 Hz, 1H), 6.67 (d, J=8.6 Hz, 2H), 6.90 (d, J=8.4 Hz, 2H), 7.12 (d, J=8.2 Hz, 2H), 7.49 (d, J=15.9 Hz, 1H), 7.58 (d, J=8.3 Hz, 2H), 9.32 (s, 1H). HRMS (EI) Calcd for C25H28O3: 376.2038 (M+). Found: 376.2046.

Workup

  1. temperatureto cool to room temperature
  2. customThe layers were separated
  3. washthe organic phase was washed with brine
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationthe filtrate was concentrated
  7. customto give the crude product
  8. customThe crude product was purified by flash chromatography on silica gel with hexanes:EtOAc (100:0 to 50:50)

Sources & evidence

ORD record
ord-3843d227bb134387a308beb40150e6a0
Source dataset
uspto-grants-2010_09
Patent number
US07799828B2

Reaction notes

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