Cesium carbonate → HCID 90408677, compound

HRID 2177593Notes

Reaction equation

HRID 2177593 reaction equation
[CH3:1][N:2]1[C:10](OS(C(F)(F)F)(=O)=O)=[C:9]2[C:4]([CH2:5][N:6]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:7][CH2:8]2)=[N:3]1.[N:26]1[CH:31]=[CH:30][CH:29]=[CH:28][C:27]=1B1OC(C)(C)C(C)(C)O1.C(=O)([O-])[O-].[Cs+].[Cs+]>CN(C=O)C.[Cu](Cl)Cl.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[CH3:1][N:2]1[C:10]([C:27]2[CH:28]=[CH:29][CH:30]=[CH:31][N:26]=2)=[C:9]2[C:4]([CH2:5][N:6]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:7][CH2:8]2)=[N:3]1

Participants

8

Reactant 3

HCID 10796Cesium carbonateHCID 11241171Pyridine-2-boronic acid, pinacol esterHCID 90409003HCID 90409003, compound

Product 1

HCID 90408677HCID 90408677, compoundYield 17.7%

Reagents, catalysts & solvents 4

HCID 24014Cupric ChlorideCatalystHCID 167845palladium(II) acetateCatalystHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of tert-butyl 2-methyl-3-(((trifluoromethyl)sulfonyl)oxy)-4,5-dihydro-2H-pyrazolo[3,4-c]pyridine-6(7H)-carboxylate (1.0 g, 2.60 mmol) in DMF (25 mL) was added pyridine-2-boronic acid pinacol ester (1.33 g, 6.49 mmol), cesium carbonate (3.42 g, 10.38 mmol), copper chloride (257 mg, 0.259 mmol), palladium acetate (29 mg, 0.130 mmol) and 1,1′-bis(diphenylphosphino)ferrocene (145 mg, 0.259 mmol). The reaction was stirred at 100° C. overnight under an atmosphere of N2. The reaction was poured into ice water and extracted with CH2Cl2 three times. The combined organic layers were dried over anhydrous MgSO4, filtered and evaporated. Chromatography on silica gel (0-100% ethyl acetatehexanes) provided the desired product (145 mg, 17%). MS (ESI) mass calcd. C17H22N4O2, 314.2. m/z found, 315.2 [M+H]+. 1H NMR (500 MHz, CDCl3) δ 8.73-8.70 (m, 0.5H), 7.80-7.76 (m, 0.5H), 7.40-7.35 (m, 2H), 7.31-7.24 (m, 1H), 4.66-4.44 (m, 2H), 4.07 (s, 2H), 3.84 (s, 1H), 3.70-3.56 (m, 2H), 2.73-2.55 (m, 2H), 1.54-1.42 (m, 9H).

Workup

  1. extractionextracted with CH2Cl2 three times
  2. dry with materialThe combined organic layers were dried over anhydrous MgSO4
  3. filtrationfiltered
  4. customevaporated

Sources & evidence

ORD record
ord-13eb0e0d33be4cc99f633157ff97edd0
Source dataset
uspto-grants-2015_06
Patent number
US09066946B2

Reaction notes

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