Cesium carbonate → HCID 57635862, compound

HRID 2109945Notes

Reaction equation

HRID 2109945 reaction equation
[C:1]([C:5]1[CH:9]=[C:8]([NH2:10])[N:7]([C:11]2[CH:16]=[C:15](C)[CH:14]=[CH:13][C:12]=2[CH3:18])[N:6]=1)([CH3:4])([CH3:3])[CH3:2].FC(F)(F)S(O[C:25]1[C:26]([C:31]([O:33][CH2:34][CH3:35])=[O:32])=[N:27][CH:28]=[CH:29][CH:30]=1)(=O)=O.[CH:38]1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.C([O-])([O-])=O.[Cs+].[Cs+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O>[C:1]([C:5]1[CH:9]=[C:8]([NH:10][C:25]2[C:26]([C:31]([O:33][CH2:34][CH3:35])=[O:32])=[N:27][CH:28]=[CH:29][CH:30]=2)[N:7]([C:11]2[C:16]([CH3:38])=[CH:15][CH:14]=[CH:13][C:12]=2[CH3:18])[N:6]=1)([CH3:3])([CH3:2])[CH3:4]

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 634876Binap, (A+-)-HCID 16769190HCID 16769190, compoundHCID 57635777HCID 57635777, compound

Product 1

HCID 57635862HCID 57635862, compoundYield 566.2%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolvent

Conditions

Temperature
110 °C

Procedure

To a dried 100 mL flask was added 3-tert-butyl-1-(2,5-dimethylphenyl)-1H-pyrazol-5-amine (1.68 g, 6.9 mmol), synthesized in the same manner as Intermediate F using Intermediate A, ethyl 3-{[(trifluoromethyl)sulfonyl]oxy}pyridine-2-carboxylate (1.88 g, 6.28 mmol) (from step 1), Pd2(dba)3 (0.28 g, 0.31 mmol), BINAP (0.39 g, 0.63 mmol), and Cs2CO3 (4.1 g, 12.5 mmol). The flask was degassed followed by addition of toluene (10 mL) and the mixture was then heated to 110° C. for 4 h. The mixture was cooled to rt, filtered through a Celite® plug with ethyl acetate as eluent, concentrated to dryness, and purified by silica gel flash chromatography with 10 to 30% of ethyl acetate in hexanes to afford 1.4 g (57%) of the desired product. 1H NMR (300 MHz, CD2Cl2) δ 9.29 (s, 1H), 8.19 (dd, 1H), 7.82 (dd, 1H), 7.41 (dd, 1H), 7.31 (dd, 1H), 7.19 (d, 2H), 6.18 (s, 1H), 4.28 (q, 2H), 2.01 (s, 6H), 1.39 (s, 9H), 1.32 (t, 3H); ES-MS m/z 393.2 (MH+); HPLC RT (min) 3.57.

Workup

  1. customsynthesized in the same manner as Intermediate F
  2. customThe flask was degassed
  3. additionfollowed by addition of toluene (10 mL)
  4. temperatureThe mixture was cooled to rt
  5. filtrationfiltered through a Celite® plug with ethyl acetate as eluent
  6. concentrationconcentrated to dryness
  7. custompurified by silica gel flash chromatography with 10 to 30% of ethyl acetate in hexanes

Sources & evidence

ORD record
ord-806d0e3b11bd4d4caee12d56dd8d95da
Source dataset
uspto-grants-2009_04
Patent number
US07517878B2

Reaction notes

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