Triethylamine → (E)-3-(3'-adamantan-1-yl-4'-hydroxybiphenyl-4-yl)acrylic acid tert-butyl ester

HRID 41720Notes

Reaction equation

HRID 41720 reaction equation
[C:1]12([C:11]3[CH:12]=[C:13]([C:18]4[CH:23]=[CH:22][C:21](Br)=[CH:20][CH:19]=4)[CH:14]=[CH:15][C:16]=3[OH:17])[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH2:2]1)[CH2:8]2.[C:25]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])(=[O:28])[CH:26]=[CH2:27].CCN(CC)CC.CN1C(=O)CCC1>[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC.C(Cl)Cl.O1CCOCC1.CC([O-])=O.CC([O-])=O.[Pd+2].O>[C:30]([O:29][C:25](=[O:28])/[CH:26]=[CH:27]/[C:21]1[CH:20]=[CH:19][C:18]([C:13]2[CH:14]=[CH:15][C:16]([OH:17])=[C:11]([C:1]34[CH2:2][CH:3]5[CH2:9][CH:7]([CH2:6][CH:5]([CH2:4]5)[CH2:10]3)[CH2:8]4)[CH:12]=2)=[CH:23][CH:22]=1)([CH3:33])([CH3:32])[CH3:31]

Participants

10

Reactant 4

HCID 8471TriethylamineHCID 13387N-methyl-2-pyrrolidoneHCID 15458tert-Butyl acrylateHCID 110363683-(Adamantan-1-yl)-4'-bromobiphenyl-4-ol

Product 1

HCID 86660473(E)-3-(3'-adamantan-1-yl-4'-hydroxybiphenyl-4-yl)acrylic acid tert-butyl esterYield 93.2%

Reagents, catalysts & solvents 5

HCID 70681Tetrabutylammonium ChlorideCatalystHCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
110 °C

Procedure

Pd(OAc)2 (6.7 mg, 0.03 mmol) was added into a flask containing a mixture of 3-adamantan-1-yl-4′-bromo-biphenyl-4-ol (1.15 g, 2.99 mmol), tert-butyl acrylate (1.75 g, 11.96 mmol), NEt3 (1.25 ml, 8.97 mmol), tetrabutylammonium chloride (1.329 g, 4.78 mmol) and NMP (3 ml). The flask, equipped with a glycol-cooled condenser, was immerged in a pre-heated oil bath (110° C.) and the reaction mixture was stirred at this temperature overnight. The mixture was allowed to return to RT and was diluted with DCM and washed with H2O. The organic phase was dried over Na2SO4 and the solvent was removed under reduced pressure. The crude reaction mixture was taken-up in dioxane (10 ml) and the resulting solution added dropwise to 40 ml of H2O. The suspension was then sonicated for 20 min and stirred overnight. After filtration of the latter, 1.2 g (93% yield) of the desired compound as a grey solid was obtained.

Workup

  1. additioncontaining
  2. temperaturecooled condenser
  3. customwas immerged in a pre-heated oil bath
  4. customto return to RT
  5. washwashed with H2O
  6. dry with materialThe organic phase was dried over Na2SO4
  7. customthe solvent was removed under reduced pressure
  8. customThe crude reaction mixture
  9. customThe suspension was then sonicated for 20 min
  10. stirringstirred overnight
  11. filtrationAfter filtration of the latter

Sources & evidence

ORD record
ord-198323b14c8d42d1a3715203dfefec38
Source dataset
uspto-grants-2013_09
Patent number
US08530517B2

Reaction notes

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