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Dichloromethane → Ethyl 6-(1-methyl-1H-pyrazol-5-yl)pyrazolo[1,5-a]pyridine-3-carboxylate

HRID 335314
Notes
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Reaction equation

HRID 335314 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]2[N:6]([N:8]=[CH:9][C:10]=2[C:11]([O:13][CH2:14][CH3:15])=[O:12])[CH:7]=1.[CH3:16][N:17]1[C:21](B2OC(C)(C)C(C)(C)O2)=[CH:20][CH:19]=[N:18]1.C(=O)([O-])[O-].[Cs+].[Cs+].C(Cl)Cl>COCCOC.O.CO.CCOC(C)=O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:16][N:17]1[C:21]([C:2]2[CH:3]=[CH:4][C:5]3[N:6]([N:8]=[CH:9][C:10]=3[C:11]([O:13][CH2:14][CH3:15])=[O:12])[CH:7]=2)=[CH:20][CH:19]=[N:18]1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

10

Reactant 4

HCID 6344Dichloromethane3×HCID 10796Cesium carbonateHCID 49129081-methyl-5-(tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole2×HCID 12208504Ethyl 6-bromopyrazolo[1,5-a]pyridine-3-carboxylate

Product 1

HCID 71283198Ethyl 6-(1-methyl-1H-pyrazol-5-yl)pyrazolo[1,5-a]pyridine-3-carboxylate

Reagents, catalysts & solvents

5
HCID 44119782Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)Catalyst3×HCID 887MethanolSolventHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

A mixture comprising ethyl 6-bromopyrazolo[1,5-a]pyridine-3-carboxylate (1.5 g, 5.57 mmol), 1-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole (1.218 g, 5.85 mmol), cesium carbonate (7.26 g, 22.30 mmol) and PdCl2(dppf).CH2Cl2 adduct (91 mg, 0.111 mmol) in DME (10 ml) and water (4.00 ml) was heated using microwave radiation at 70° C. for 1 hr. Further PdCl2(dppf).CH2Cl2 adduct (91 mg, 0.111 mmol) was added and the mixture was heated at 80° C. for 1 hr. 1-Methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole (1.218 g, 5.85 mmol) and PdCl2(dppf).CH2Cl2 adduct (91 mg, 0.111 mmol) were added and heating continued at 100° C. for 3 hrs. The mixture was diluted with 10% MeOH in EtOAc (200 ml) and washed with sat. NaHCO3. The organic solvent was removed under vacuum and azeotroped with toluene. The resulting solid was loaded onto silica and purified by chromatography eluting with 0-100% EtOAc in iso-hexane to afford the title compound;

Workup

  1. customat 70° C.
  2. customfor 1 hr
  3. temperatureheating
  4. washwashed with sat. NaHCO3
  5. customThe organic solvent was removed under vacuum
  6. customazeotroped with toluene
  7. custompurified by chromatography
  8. washeluting with 0-100% EtOAc in iso-hexane

Sources & evidence

ORD record
ord-a51e8a8797644202b84ed8ddc75e957f
Source dataset
uspto-grants-2014_11
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08883819B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes