Tetrabutylammonium Fluoride → HCID 59699794, compound

HRID 603045Notes

Reaction equation

HRID 603045 reaction equation
[CH3:1][C:2](C)([O-])C.[Na+].Br[C:8]1[CH:9]=[C:10]2[C:16]([C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=3[O:23][CH3:24])=[CH:15][N:14]([Si](C(C)C)(C(C)C)C(C)C)[C:11]2=[N:12][CH:13]=1.[F-].C([N+:40]([CH2:49][CH2:50][CH2:51][CH3:52])([CH2:45]CCC)CCCC)CCC.[Na]>O1CCOCC1.CNC1C=CC=CC=1.C1COCC1.C(P[Pd-2]PC(C)(C)C)(C)(C)C.CO>[CH3:24][O:23][C:18]1[CH:19]=[CH:20][CH:21]=[CH:22][C:17]=1[C:16]1[C:10]2[C:11](=[N:12][CH:13]=[C:8]([N:40]([CH3:45])[C:49]3[CH:50]=[CH:51][CH:52]=[CH:2][CH:1]=3)[CH:9]=2)[NH:14][CH:15]=1

Participants

10

Reactant 4

HCID 2724141Tetrabutylammonium FluorideHCID 5360545SodiumHCID 23676156Sodium t-butoxideHCID 59699882HCID 59699882, compound

Product 1

HCID 59699794HCID 59699794, compoundYield 64%

Reagents, catalysts & solvents 5

HCID 178454914HCID 178454914, compoundCatalystHCID 887MethanolSolventHCID 7515N-MethylanilineSolventHCID 8028TetrahydrofuranSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
130 °C

Procedure

30 mg of sodium-tert-butoxide and 12 mg of bis(tert-butylphosphino)palladium(0) were placed in a Smith® vial and the vial flushed with nitrogen, 100 mg (0.22 mmol) of 5-bromo-3-(2-methoxy-phenyl)-1-triisopropylsilanyl-1H-pyrrolo[2,3-b]pyridine in 1 ml of anhydrous 1,4-dioxane and 35 μl of N-methylaniline were added and the resulting mixture heated to 130° C. for 15 h. The reaction mixture was then cooled to ambient temperature and 0.4 ml of a 1M solution of tetra-n-butylammonium fluoride in THF added. The mixture was stirred at room temperature for 2 h, 2 ml of methanol and amberlyst strongly acidic ion exchange resin, loaded with sodium was added. After shaking at room temperature for 2 h the crude material is directly adsorbed onto silica gel and purified by flash chromatography on silica gel using a gradient of ethyl acetate in hexanes to afford 42 mg (0.14 mmol; 64% yield) of [3-(2-methoxy-phenyl)-1H-pyrrolo[2,3-b]pyridine-5-yl]-methyl-phenyl-amine as a brown residue. 1H-NMR (d6-DMSO); δ 11.88 (s, 1H), 8.11 (d, J=2.5 Hz, 1H), 7.75 (d, J=2.4 Hz, 1H), 7.70 (d, J=2.5 Hz, 1H), 7.48 (dd, J=1.5 Hz, 7.3 Hz, 1H), 7.26 (ddd. J=1.5 Hz, 8.3 Hz, 1H), 7.16 (t, J=7.9 Hz, 2H), 7.08 (d. J=8.3 Hz, 1H), 7.00 (t(d), J=0.9 Hz, 8.3 Hz, 1H), 6.72-6.68 (m, 3H), 3.76 (s, 3H), 3.29 (s, 3H); MS: m/z 330 [MH+].

Workup

  1. additionwere added
  2. temperatureThe reaction mixture was then cooled to ambient temperature
  3. additionwas added
  4. custompurified by flash chromatography on silica gel using a gradient of ethyl acetate in hexanes

Sources & evidence

ORD record
ord-07829a8ee00e48b5abdd66bb2924bc75
Source dataset
uspto-grants-2011_03
Patent number
US07906648B2

Reaction notes

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