Potassium Carbonate → 4-[3-(1-Adamantyl)-4-(t-butyldimethylsilyloxy)phenyl]-benzaldehyde

HRID 860549Notes

Reaction equation

HRID 860549 reaction equation
[CH:1]([C:3]1[CH:8]=[CH:7][C:6](B(O)O)=[CH:5][CH:4]=1)=[O:2].[C:12]12([C:22]3[CH:23]=[C:24](Br)[CH:25]=[CH:26][C:27]=3[O:28][Si:29]([C:32]([CH3:35])([CH3:34])[CH3:33])([CH3:31])[CH3:30])[CH2:21][CH:16]3[CH2:17][CH:18]([CH2:20][CH:14]([CH2:15]3)[CH2:13]1)[CH2:19]2.C(=O)([O-])[O-].[K+].[K+]>C1(C)C=CC=CC=1.CO.O.C(OCC)(=O)C.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:12]12([C:22]3[CH:23]=[C:24]([C:6]4[CH:7]=[CH:8][C:3]([CH:1]=[O:2])=[CH:4][CH:5]=4)[CH:25]=[CH:26][C:27]=3[O:28][Si:29]([C:32]([CH3:35])([CH3:34])[CH3:33])([CH3:30])[CH3:31])[CH2:13][CH:14]3[CH2:20][CH:18]([CH2:17][CH:16]([CH2:15]3)[CH2:21]1)[CH2:19]2

Participants

8

Reactant 3

HCID 11430Potassium CarbonateHCID 5910734-Formylphenylboronic AcidHCID 107883163-(1-Adamantyl)-4-(t-butyldimethylsilyloxy)bromobenzene

Product 1

HCID 113853054-[3-(1-Adamantyl)-4-(t-butyldimethylsilyloxy)phenyl]-benzaldehydeYield 78%

Reagents, catalysts & solvents 4

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 21867641Toluene methanolSolvent

Procedure

A mixture of 4-formylphenyl boronic acid (0.301 g, 2.00 mmol), 3-(1-adamantyl)-4-(t-butyldimethylsilyloxy)bromobenzene (0.768 g, 1.82 mmol, prepared in a similar manner as described by Charpentier, B. et al. in J. Med. Chem. 1995, 38, 4993–5006) and potassium carbonate (0.757 g, 5.47 mmol) in 60 mL of toluene:methanol (4:1) and water (2 mL) was degassed with argon for 30 minutes. Tetrakis(triphenylphosphine) palladium(0) (0.422 g, 0.36 mmol) was added and the mixture heated at reflux for 19 hours. The solution was cooled to room temperature, diluted with ethyl acetate and washed successively with water and brine, dried over anhydrous magnesium sulfate, filtered and evaporated. The residue was purified on silica gel (eluent: hexane:EtOAc, 97:3) to give 0.500 g of 4-[3-(1-adamantyl)-4-(t-butyldimethylsilyloxy)phenyl]-benzaldehyde (78%) as a solid. 1H NMR (300 MHz; CDCl3): 0.38 (s, 6H), 1.07 (s, 9H), 1.79 (s, 6H), 2.10–2.17 (m, 9H), 6.89 (d, J=8.7 Hz, 1H), 7.34 (dd, J1=8.4 Hz, J2=2.4 Hz, 1H), 7.52 (d, J=2.4 Hz, 1H), 7.71 (d, J=8.1 Hz, 2H), 7.91 (d, J=8.1 Hz, 2H), 10.02 (brs, 1H).

Workup

  1. customprepared in a similar manner
  2. temperaturethe mixture heated
  3. temperatureat reflux for 19 hours
  4. washwashed successively with water and brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. filtrationfiltered
  7. customevaporated
  8. customThe residue was purified on silica gel (eluent: hexane:EtOAc, 97:3)

Sources & evidence

ORD record
ord-1c8da66cc81748a0a8a579bab108a655
Source dataset
uspto-grants-2006_12
Patent number
US07153875B2

Reaction notes

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