Tetrabutylammonium Fluoride → (E)-isopropyl 3-(4-((6-hydroxy-2-(2-isopropylphenyl)benzo[b]thiophen-3-yl)oxy)phenyl)acrylate

HRID 632705Notes

Reaction equation

HRID 632705 reaction equation
[Si]([O:8][C:9]1[CH:10]=[CH:11][C:12]2[C:16]([O:17][C:18]3[CH:23]=[CH:22][C:21](/[CH:24]=[CH:25]/[C:26]([O:28][CH:29]([CH3:31])[CH3:30])=[O:27])=[CH:20][CH:19]=3)=[C:15]([C:32]3[CH:37]=[CH:36][CH:35]=[CH:34][C:33]=3[CH:38]([CH3:40])[CH3:39])[S:14][C:13]=2[CH:41]=1)(C(C)(C)C)(C)C.[F-].C([N+](CCCC)(CCCC)CCCC)CCC>C1COCC1>[OH:8][C:9]1[CH:10]=[CH:11][C:12]2[C:16]([O:17][C:18]3[CH:19]=[CH:20][C:21](/[CH:24]=[CH:25]/[C:26]([O:28][CH:29]([CH3:31])[CH3:30])=[O:27])=[CH:22][CH:23]=3)=[C:15]([C:32]3[CH:37]=[CH:36][CH:35]=[CH:34][C:33]=3[CH:38]([CH3:40])[CH3:39])[S:14][C:13]=2[CH:41]=1

Participants

4

Reactant 2

HCID 2724141Tetrabutylammonium FluorideHCID 131735441(E)-isopropyl 3-(4-((6-((tert-butyldimethylsilyl)oxy)-2-(2-isopropylphenyl)benzo[b]thiophen-3-yl)oxy)phenyl)acrylate

Product 1

HCID 90372198(E)-isopropyl 3-(4-((6-hydroxy-2-(2-isopropylphenyl)benzo[b]thiophen-3-yl)oxy)phenyl)acrylateYield 49%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of (E)-isopropyl 3-(4-((6-((tert-butyldimethylsilyl)oxy)-2-(2-isopropylphenyl)benzo[b]thiophen-3-yl)oxy)phenyl)acrylate (35 mg, 0.060 mmol) in THF (2.0 mL) at 0° C. was added tetra-n-butylammonium fluoride (1.0 M in THF, 0.089 mL, 0.089 mmol) dropwise, the reaction immediately turned bright yellow in color. Stirring was continued at 0° C. for 45 min after which the reaction was warmed to room temperature for 15 min and then quenched by addition of st. aq. NaHCO3. The aqueous layer was extracted with EtOAc (4×) and the combined organic layers were dried over anhydrous MgSO4, filtered and concentrated in vacuo. The resulting crude material was purified by column chromatography (SiO2, 0-20% EtOAc/Heptane) to afford (E)-isopropyl 3-(4-((6-hydroxy-2-(2-isopropylphenyl)benzo[b]thiophen-3-yl)oxy)phenyl)acrylate (14.0 mg, 0.029 mmol, 49% yield). 1H NMR (400 MHz, CD3OD) δ ppm=7.55 (d, J=16.0 Hz, 1H), 7.45 (d, J=8.8 Hz, 2H), 7.37-7.20 (m, 5H), 7.11 (td, J=7.6, 1.5 Hz, 1H), 6.89-6.81 (m, 3H), 6.32 (d, J=16.0 Hz, 11H), 5.05 (p, J=6.2 Hz, 1H), 3.23 (p, J=6.9 Hz, 1H), 1.28 (d, J=6.2 Hz, 6H), 1.16 (d, J=6.8 Hz, 6H). HRMS (m/z, MH+): 473.1774.

Workup

  1. customthe reaction immediately turned bright yellow in color
  2. customquenched by addition of st
  3. extractionThe aqueous layer was extracted with EtOAc (4×)
  4. dry with materialthe combined organic layers were dried over anhydrous MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe resulting crude material was purified by column chromatography (SiO2, 0-20% EtOAc/Heptane)

Sources & evidence

ORD record
ord-ae83859118484af09bc8a137f63e6e48
Source dataset
uspto-grants-2016_04
Patent number
US09321746B2

Reaction notes

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