Cesium carbonate → methyl 4-(4-ethenyl-1-methyl-1H-pyrazol-5-yl)-2-thiophenecarboxylate

HRID 2392166Notes

Reaction equation

HRID 2392166 reaction equation
Br[C:2]1[CH:3]=[N:4][N:5]([CH3:16])[C:6]=1[C:7]1[CH:8]=[C:9]([C:12]([O:14][CH3:15])=[O:13])[S:10][CH:11]=1.N1C=CC=[CH:19][CH:18]=1.C(B1OB(C=C)OB(C=C)O1)=C.C([O-])([O-])=O.[Cs+].[Cs+]>O1CCOCC1.O.CC(C)([P](C(C)(C)C)([Pd][P](C(C)(C)C)(C(C)(C)C)C(C)(C)C)C(C)(C)C)C>[CH:18]([C:2]1[CH:3]=[N:4][N:5]([CH3:16])[C:6]=1[C:7]1[CH:8]=[C:9]([C:12]([O:14][CH3:15])=[O:13])[S:10][CH:11]=1)=[CH2:19]

Participants

7

Reactant 3

HCID 10796Cesium carbonateHCID 27348062,4,6-Trivinylboroxin-Pyridine ComplexHCID 57826395methyl 4-(4-bromo-1-methyl-1H-pyrazol-5-yl)-2-thiophenecarboxylate

Product 1

HCID 57826468methyl 4-(4-ethenyl-1-methyl-1H-pyrazol-5-yl)-2-thiophenecarboxylate

Reagents, catalysts & solvents 3

HCID 178418851HCID 178418851, compoundCatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
70 °C

Procedure

To a 5 mL sealed tube reactor was added methyl 4-(4-bromo-1-methyl-1H-pyrazol-5-yl)-2-thiophenecarboxylate (473 mg, 1.57 mmol) [prepared according to the procedure of Example 156], pyridine-triethenylboroxine (1:1) (666 mg, 2.77 mmol), Pd(PtBu3)2 (16.8 mg, 0.03 mmol) and Cs2CO3 (1.72 g, 5.28 mmol) in 1,4-Dioxane (6.3 mL) and water (1.6 mL). The reaction was heated at 70° C. for 2 hours and partitioned between CHCl3 (75 mL)/H2O (75 mL). The organic layer was dried with Na2SO4, adsorbed onto silica and purified via column chromatography (25-70% EtOAc/Hexane) affording the desired product: LC-MS (ES) m/z=249 (M+H)+.

Workup

  1. customTo a 5 mL sealed tube reactor
  2. customprepared
  3. custompartitioned between CHCl3 (75 mL)/H2O (75 mL)
  4. dry with materialThe organic layer was dried with Na2SO4
  5. custompurified via column chromatography (25-70% EtOAc/Hexane)

Sources & evidence

ORD record
ord-2f46f635b14a4d2fbebdb3df578268cd
Source dataset
uspto-grants-2012_09
Patent number
US08273782B2

Reaction notes

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