Cesium carbonate → HCID 10114171, compound

HRID 861153Notes

Reaction equation

HRID 861153 reaction equation
Cl[C:2]1[N:7]2[N:8]=[C:9]([C:23]3[CH:28]=[CH:27][C:26]([O:29][CH3:30])=[CH:25][CH:24]=3)[C:10]([C:11]3[CH:16]=[CH:15][N:14]=[C:13]([NH:17][CH:18]4[CH2:22][CH2:21][CH2:20][CH2:19]4)[N:12]=3)=[C:6]2[CH:5]=[CH:4][CH:3]=1.C(=O)([O-])[O-].[Cs+].[Cs+].[CH:37]1([NH2:40])[CH2:39][CH2:38]1>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1C=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>[CH:18]1([NH:17][C:13]2[N:12]=[C:11]([C:10]3[C:9]([C:23]4[CH:24]=[CH:25][C:26]([O:29][CH3:30])=[CH:27][CH:28]=4)=[N:8][N:7]4[C:2]([NH:40][CH:37]5[CH2:39][CH2:38]5)=[CH:3][CH:4]=[CH:5][C:6]=34)[CH:16]=[CH:15][N:14]=2)[CH2:22][CH2:21][CH2:20][CH2:19]1

Participants

7

Reactant 3

HCID 10796Cesium carbonateHCID 69828CyclopropylamineHCID 57444748HCID 57444748, compound

Product 1

HCID 10114171HCID 10114171, compoundYield 73.2%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 634876Binap, (A+-)-CatalystHCID 1140TolueneSolvent

Procedure

To a solution of 4-[7-chloro-2-(4-methoxyphenyl)pyrazolo[1,5-a]pyridin-3-yl]-N-cyclopentyl-2-pyrimidinamine (0.39 g, 0.93 mmol) in toluene (20 mL) was added successively racemic-BINAP (34.7 mg, 0.06 mmol), cesium carbonate (0.91 g, 2.8 mmol), cyclopropylamine (0.64 mL, 9.3 mmol) and palladium (II) acetate (8.3 mg, 0.04 mmol). The resultant mixture was heated under reflux for 8 hours. After cooling to room temperature the reaction mixture was partitioned between ether and water. The organic layer was washed with brine and dried over magnesium sulfate. Filtration and concentration followed by flash chromatography (3:1 hexanes-ethyl acetate) provided 3-[2-(cyclopentylamino)-4-pyrimidinyl]-N-cyclopropyl-2-(4-methoxyphenyl)pyrazolo-[1,5-a]pyridin-7-amine (0.30 g, 73%) as a pale yellow solid. 1H NMR (CDCl3): δ 7.95 (d, 1 H), 7.85 (d, 1 H), 7.56 (d, 2 H), 7.36 (t, 1 H), 6.99 (d, 2 H), 6.40 (d, 1 H), 6.33 (m, 2 H), 4.38 (m, 1 H), 3.88 (s, 3 H), 2.68 (m, 1 H), 2.09 (m, 2H), 1.81–1.57 (m, 6 H), 0.89 (m, 2 H), 0.75 (m, 2 H); MS m/z 441 (M+1).

Workup

  1. temperatureunder reflux for 8 hours
  2. customwas partitioned between ether and water
  3. washThe organic layer was washed with brine
  4. dry with materialdried over magnesium sulfate
  5. filtrationFiltration and concentration

Sources & evidence

ORD record
ord-7b16a1aa9abc434c94c9dbb3bcd7f6be
Source dataset
uspto-grants-2006_12
Patent number
US07153855B2

Reaction notes

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