Triethylamine → HCID 66839059, compound

HRID 546783Notes

Reaction equation

HRID 546783 reaction equation
Br[C:2]1[N:7]=[C:6]([F:8])[C:5]([N:9]2[CH:13]=[C:12]([CH3:14])[N:11]=[CH:10]2)=[CH:4][CH:3]=1.[F:15][C:16]([F:35])([F:34])[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[CH:23]1[CH2:28][CH2:27][CH2:26][N:25]2[N:29]=[C:30]([CH:32]=[CH2:33])[N:31]=[C:24]12.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(N(CC)CC)C>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O.C(OCC)(=O)C>[F:8][C:6]1[N:7]=[C:2](/[CH:33]=[CH:32]/[C:30]2[N:31]=[C:24]3[CH:23]([C:18]4[CH:19]=[CH:20][CH:21]=[CH:22][C:17]=4[C:16]([F:34])([F:15])[F:35])[CH2:28][CH2:27][CH2:26][N:25]3[N:29]=2)[CH:3]=[CH:4][C:5]=1[N:9]1[CH:13]=[C:12]([CH3:14])[N:11]=[CH:10]1

Participants

9

Reactant 4

HCID 8471TriethylamineHCID 80271Tri-o-tolylphosphineHCID 66839044HCID 66839044, compoundHCID 86628517HCID 86628517, compound

Product 1

HCID 66839059HCID 66839059, compoundYield 22.8%

Reagents, catalysts & solvents 4

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
120 °C

Procedure

6-Bromo-2-fluoro-3-(4-methyl-1H-imidazol-1-yl)pyridine (156 mg) and 8-(2-trifluoromethylphenyl)-2-vinyl-5,6,7,8-tetrahydro[1,2,4]triazolo[1,5-a]pyridine (179 mg) were dissolved in toluene (5 ml). Tris(dibenzylideneacetone)dipalladium (167 mg), tri-o-tolylphosphine (111 mg) and triethylamine (340 ul) were added and the reaction solution was heated and stirred in a nitrogen atmosphere at 120° C. for 1.3 hours. After leaving to cool, ethyl acetate and water were added. The reaction solution was filtered through celite and the organic layer was separated. The resulting organic layer was washed with brine and then dried over anhydrous sodium sulfate. The drying agent was separated by filtration, and then the organic layer was concentrated under reduced pressure. The residue was purified by NH silica gel column chromatography to obtain a racemate of the title compound (65 mg). The resulting racemate was separated by CHIRALPAK™ IB manufactured by Daicel Chemical Industries, Ltd. (2 cm×25 cm; mobile phase: hexane:ethanol=6:4) to obtain the title optically active compound with positive optical rotation (20 mg, >99% ee) and the title optically active compound with negative optical rotation (20 mg, >99% ee).

Workup

  1. temperaturethe reaction solution was heated
  2. customAfter leaving
  3. temperatureto cool
  4. filtrationThe reaction solution was filtered through celite
  5. customthe organic layer was separated
  6. washThe resulting organic layer was washed with brine
  7. dry with materialdried over anhydrous sodium sulfate
  8. customThe drying agent was separated by filtration
  9. concentrationthe organic layer was concentrated under reduced pressure
  10. customThe residue was purified by NH silica gel column chromatography

Sources & evidence

ORD record
ord-6323da42432c4bb9b7c1afcb4f14ad51
Source dataset
uspto-grants-2011_05
Patent number
US07935815B2

Reaction notes

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