Bromine → HCID 67301096, compound

HRID 2386188Notes

Reaction equation

HRID 2386188 reaction equation
[Si:1]([O:8][CH:9]([C:22]1[O:23][CH:24]=[CH:25][N:26]=1)[CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[Li]C(C)(C)C.[Br:32]Br>C1COCC1.CCOC(C)=O>[Br:32][C:24]1[O:23][C:22]([CH:9]([O:8][Si:1]([C:4]([CH3:7])([CH3:5])[CH3:6])([CH3:2])[CH3:3])[CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)=[N:26][CH:25]=1

Participants

6

Reactant 3

HCID 24408BromineHCID 685237222-(1-{[tert-Butyl(dimethyl)silyl]oxy}-7-phenylheptyl)-1,3-oxazoleHCID 178418306HCID 178418306, compound

Product 1

HCID 67301096HCID 67301096, compoundYield 90%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

2-(1-(tert-Butyldimethylsilyloxy)-7-phenylheptyl)oxazole (201 mg, 0.554 mmol) was dissolved in anhydrous THF (5 mL), cooled to −78° C. and t-BuLi (1.7 M in pentane, 1.3 equiv) was added dropwise under Ar. The reaction mixture was stirred for 2 h at −40° C., cooled to −78° C. and bromine (3 equiv) was added dropwise. The reaction mixture was warmed to room temperature, diluted with EtOAc, washed with saturated Na2S2O3, washed with saturated aqueous NaCl and dried over Na2SO4. Evaporation in vacuo yielded the crude aryl bromide, which was purified by flash chromatography (0-1.5% EtOAc/hexanes) to afford the title compound as a clear oil (218 mg, 90%): 1H NMR (CDCl3, 600 MHz) 7.28-7.26 (m, 2H), 7.17-7.16 (m, 3H), 6.92 (s, 1H), 4.74 (t, 1H, J=7.2 Hz), 2.59 (t, 2H, J=7.8 Hz), 1.90-1.79 (m, 2H), 1.60-1.59 (m, 2H), 1.53-1.34 (m, 6H), 0.88 (s, 9H), 0.07 (s, 3H), −0.02 (s, 3H); 13C NMR (CDCl3, 150 MHz) δ 167.8, 143.6, 129.3, 129.1, 127.7, 126.5, 122.1, 69.5, 37.0, 36.8, 32.3, 30.0, 26.6, 26.6, 25.9, 19.1, −4.1, −4.3.

Workup

  1. temperaturecooled to −78° C.
  2. temperatureThe reaction mixture was warmed to room temperature
  3. washwashed with saturated Na2S2O3
  4. washwashed with saturated aqueous NaCl
  5. dry with materialdried over Na2SO4
  6. customEvaporation in vacuo
  7. customyielded the crude aryl bromide, which
  8. customwas purified by flash chromatography (0-1.5% EtOAc/hexanes)

Sources & evidence

ORD record
ord-5bf1ad86a0e7403a934f600ef10613d6
Source dataset
uspto-grants-2012_09
Patent number
US08268817B2

Reaction notes

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