Tetrabutylammonium Fluoride → HCID 59129375, compound

HRID 468381Notes

Reaction equation

HRID 468381 reaction equation
[CH2:1]([O:3][C:4](=[O:31])[CH2:5][C:6]([CH3:30])([CH3:29])[C:7]#[C:8][C:9]1[CH:14]=[C:13]([N+:15]([O-:17])=[O:16])[CH:12]=[CH:11][C:10]=1[NH:18][CH2:19][CH2:20][O:21][Si](C(C)(C)C)(C)C)[CH3:2].CCCC[N+](CCCC)(CCCC)CCCC.[F-]>CC#N.Cl[Pd]Cl>[CH2:1]([O:3][C:4](=[O:31])[CH2:5][C:6]([C:7]1[N:18]([CH2:19][CH2:20][OH:21])[C:10]2[C:9]([CH:8]=1)=[CH:14][C:13]([N+:15]([O-:17])=[O:16])=[CH:12][CH:11]=2)([CH3:30])[CH3:29])[CH3:2]

Participants

5

Reactant 2

HCID 2724141Tetrabutylammonium FluorideHCID 59129165HCID 59129165, compound

Product 1

HCID 59129375HCID 59129375, compoundYield 60.3%

Reagents, catalysts & solvents 2

HCID 24290Palladium ChlorideCatalystHCID 6342AcetonitrileSolvent

Procedure

A solution of 5-{2-[2-(tert-butyl-dimethyl-silanyloxy)-ethylamino]-5-nitro-phenyl}-3,3-dimethyl-pent-4-ynoic acid ethyl ester (600 mg, 1.34 mmol) and PdCl2 (650 mg) in CH3CN (30 mL) was heated at reflux overnight. The resulting mixture was extracted with EtOAc (30 mL×3). The combined organic extracts were dried over anhydrous Na2SO4 and evaporated under vacuum. The residue was dissolved in THF (20 mL) and TBAF (780 mg, 3.0 mmol) was added. The mixture was stirred at room temperature for 1 h, the solvent was removed under vacuum, and the residue was purified by chromatography on silica gel (10% ethyl acetate/petroleum) to afford 3-[1-(2-hydroxy-ethyl)-5-nitro-1H-indol-2-yl]-3-methyl-butyric acid ethyl ester (270 mg, 60%). 1H NMR (300 MHz, CDCl3) δ 8.45 (d, J=2.1 Hz, 1H), 8.05 (dd, J=2.1, 9.0 Hz, 1H), 6.36 (d, J=9.0 Hz, 1H), 6.48 (s, 1H), 4.46 (t, J=6.6 Hz, 2H), 4.00-3.91 (m, 4H), 2.76 (s, 2H), 1.61 (5, 6H), 0.99 (t, J=7.2 Hz, 1H), 0.85 (s, 9H), 0.03 (s, 6H).

Workup

  1. temperatureat reflux overnight
  2. extractionThe resulting mixture was extracted with EtOAc (30 mL×3)
  3. dry with materialThe combined organic extracts were dried over anhydrous Na2SO4
  4. customevaporated under vacuum
  5. dissolutionThe residue was dissolved in THF (20 mL)
  6. customthe solvent was removed under vacuum
  7. customthe residue was purified by chromatography on silica gel (10% ethyl acetate/petroleum)

Sources & evidence

ORD record
ord-cfbc7bebf7c846f3b0bdfc832afae3fa
Source dataset
uspto-grants-2014_01
Patent number
US08623905B2

Reaction notes

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