Tetrabutylammonium Fluoride → HCID 67089413, compound

HRID 661093Notes

Reaction equation

HRID 661093 reaction equation
[C:1]([O:7][CH2:8][C@H:9]([C:27]1[CH:32]=[CH:31][C:30]([C:33]([F:36])([F:35])[F:34])=[CH:29][CH:28]=1)[C@H:10]([C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[CH2:11][O:12][Si](C(C)(C)C)(C)C)(=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3].CCCC[N+](CCCC)(CCCC)CCCC.[F-]>C1COCC1>[C:1]([O:7][CH2:8][C@H:9]([C:27]1[CH:32]=[CH:31][C:30]([C:33]([F:34])([F:35])[F:36])=[CH:29][CH:28]=1)[C@H:10]([C:20]([O:22][C:23]([CH3:25])([CH3:26])[CH3:24])=[O:21])[CH2:11][OH:12])(=[O:6])[C:2]([CH3:3])([CH3:4])[CH3:5]

Participants

4

Reactant 2

HCID 2724141Tetrabutylammonium Fluoride2×HCID 67089418HCID 67089418, compound

Product 1

HCID 67089413HCID 67089413, compoundYield 89.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

(2S,3S)-3-(Tert-butoxycarbonyl)-4-(tert-butyldimethylsilyloxy)-2-(4-(trifluoromethyl)phenyl)butyl pivalate (2.2 g, 4.0 mmol) was taken up in 40 mL of THF and chilled to 0° C. TBAF, 1 M in THF (6.0 mL, 6.0 mmol) was added slowly. After 20 minutes, the mixture was warmed to room temperature and stirred for 1 hour. 0.5 mL of additional TBAF was added, and the mixture was stirred for 20 minutes. The mixture was quenched with 20 mL of aq NH4Cl. The mixture was then diluted with 40 mL of water and extracted twice with 50 mL of EtOAc. The combined organic extracts were washed with 50 mL of brine and dried over MgSO4. Filtration and concentration under reduced pressure, followed by flash chromatography on silica gel (5% to 40% EtOAc/hexanes) afforded (2S,3S)-3-(tert-butoxycarbonyl)-4-hydroxy-2-(4-(trifluoromethyl)phenyl)butyl pivalate (1.5 g, 86% yield) as a yellow solid. 1H NMR (400 MHz, CDCl3) δ ppm 7.59 (d, J=8.22 Hz, 2H) 7.37 (d, J=8.02 Hz, 2H) 4.57 (d, J=6.4 Hz, 1H) 4.45-4.35 (m, 2H) 4.06 (s, 1H) 3.70 (s, 2H) 3.51-3.41 (m, 1H), 1.75 (broad s, 1H) 1.33 (s, 9H) 1.08 (s, 9H).

Workup

  1. temperaturethe mixture was warmed to room temperature
  2. stirringthe mixture was stirred for 20 minutes
  3. customThe mixture was quenched with 20 mL of aq NH4Cl
  4. additionThe mixture was then diluted with 40 mL of water
  5. extractionextracted twice with 50 mL of EtOAc
  6. washThe combined organic extracts were washed with 50 mL of brine
  7. dry with materialdried over MgSO4
  8. filtrationFiltration and concentration under reduced pressure

Sources & evidence

ORD record
ord-ef57e10650274cb1a2720a0a5fa88c6e
Source dataset
uspto-grants-2011_12
Patent number
US08084479B2

Reaction notes

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