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Cesium carbonate → 6-(1-tert-butyl-1H-pyrazol-4-yl)-3-methyl-4-(methylthio)-3H-imidazo[4,5-c]pyridine

HRID 2209011
Notes
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Reaction equation

HRID 2209011 reaction equation
Cl[C:2]1[N:7]=[C:6]([S:8][CH3:9])[C:5]2[N:10]([CH3:13])[CH:11]=[N:12][C:4]=2[CH:3]=1.ClC1N=C(SC)C2N=CN(C)C=2C=1.[C:27]([N:31]1[CH:35]=[C:34](C2OC(C)(C)C(C)(C)O2)[CH:33]=[N:32]1)([CH3:30])([CH3:29])[CH3:28].C([O-])([O-])=O.[Cs+].[Cs+]>C(C1C=CC=C(C(C)C)C=1N1C=CN(C2C(C(C)C)=CC=CC=2C(C)C)C1=[Pd-3](Cl)(Cl)C1C(Cl)=CC=CN=1)(C)C.O.COCCOC>[C:27]([N:31]1[CH:35]=[C:34]([C:2]2[N:7]=[C:6]([S:8][CH3:9])[C:5]3[N:10]([CH3:13])[CH:11]=[N:12][C:4]=3[CH:3]=2)[CH:33]=[N:32]1)([CH3:30])([CH3:29])[CH3:28]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 1178431521-tert-butyl-4-(4,4,5,5-tetramethyl-1,3-dioxolan-2-yl)-1H-pyrazoleHCID 1178433356-chloro-1-methyl-4-(methylthio)-1H-imidazo[4,5-c]pyridineHCID 1178434146-chloro-3-methyl-4-(methylthio)-3H-imidazo[4,5-c]pyridine

Product 1

HCID 1178438386-(1-tert-butyl-1H-pyrazol-4-yl)-3-methyl-4-(methylthio)-3H-imidazo[4,5-c]pyridine

Reagents, catalysts & solvents 3

HCID 178439029HCID 178439029, compoundCatalystHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent

Procedure

To a mixture of 6-chloro-3-methyl-4-(methylthio)-3H-imidazo[4,5-c]pyridine 2.02 and 6-chloro-1-methyl-4-(methylthio)-1H-imidazo[4,5-c]pyridine 2.03 (prepared as previously described, ˜1:2 mixture of regioisomers, 1.25 g, 5.85 mmol),1-tert-butyl-4-(4,4,5,5-tetramethyl-1,3-dioxolan-2-yl)-1H-pyrazole (2.20 g, 8.78 mmol), and Cs2CO3 (5.72 g, 17.6 mmol) was added DME (20 mL) and water (10 mL) and the solution was degassed for 10 min. [1,3-Bis(2,6-Diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(II) dichloride (397 mg, 0.585 mmol) was added and the reaction was heated to 100 deg C. for 1 hour. Upon cooling, the aqueous layer was removed, EtOAc and water were added, and the layers separated. The organic layer was dried (MgSO4), filtered and concentrated. The residue was purified by flash chromatography (EtOAc 0-->5% MeOH gradient) to afford 6-(1-tert-butyl-1H-pyrazol-4-yl)-3-methyl-4-(methylthio)-3H-imidazo[4,5-c]pyridine 2.39 and 6-(1-tert-butyl-1H-pyrazol-4-yl)-3-methyl-4-(methylthio)-3H-imidazo[4,5-c]pyridine 2.40, which were isolated as a mixture and carried directly into the next step.

Workup

  1. customprepared
  2. additionwas added
  3. temperaturethe reaction was heated to 100 deg C
  4. temperatureUpon cooling
  5. customthe aqueous layer was removed
  6. additionEtOAc and water were added
  7. customthe layers separated
  8. dry with materialThe organic layer was dried (MgSO4)
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe residue was purified by flash chromatography (EtOAc 0-->5% MeOH gradient)

Sources & evidence

ORD record
ord-66678d11df444beb935874d4c5aa8a06
Source dataset
uspto-grants-2016_06
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US09376441B2

Reaction notes

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