2-(Di-tert-butylphosphino)biphenyl → 9-(4-tert-butylpyridin-2-yl)-2-(3-(4-phenyl-1H-pyrazol-1-yl)phenoxy)-9H-carbazole

HRID 1509650Notes

Reaction equation

HRID 1509650 reaction equation
[C:1]1([C:7]2[CH:8]=[N:9][N:10]([C:12]3[CH:13]=[C:14]([CH:29]=[CH:30][CH:31]=3)[O:15][C:16]3[CH:28]=[CH:27][C:26]4[C:25]5[C:20](=[CH:21][CH:22]=[CH:23][CH:24]=5)[NH:19][C:18]=4[CH:17]=3)[CH:11]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.CC(P(C(C)(C)C)C1C(C2C=CC=CC=2)=CC=CC=1)(C)C.CC([O-])(C)C.[Na+].Br[C:60]1[CH:65]=[C:64]([C:66]([CH3:69])([CH3:68])[CH3:67])[CH:63]=[CH:62][N:61]=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].O1CCOCC1.C1(C)C=CC=CC=1>[C:66]([C:64]1[CH:63]=[CH:62][N:61]=[C:60]([N:19]2[C:18]3[CH:17]=[C:16]([O:15][C:14]4[CH:29]=[CH:30][CH:31]=[C:12]([N:10]5[CH:11]=[C:7]([C:1]6[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=6)[CH:8]=[N:9]5)[CH:13]=4)[CH:28]=[CH:27][C:26]=3[C:25]3[C:20]2=[CH:21][CH:22]=[CH:23][CH:24]=3)[CH:65]=1)([CH3:69])([CH3:68])[CH3:67]

Participants

8

Reactant 4

HCID 27342152-(Di-tert-butylphosphino)biphenylHCID 131833052-Bromo-4-tert-butylpyridineHCID 23676156Sodium t-butoxideHCID 1177296942-(3-(4-phenyl-1H-pyrazol-1-yl)phenoxy)-9H-carbazole

Product 1

HCID 863432229-(4-tert-butylpyridin-2-yl)-2-(3-(4-phenyl-1H-pyrazol-1-yl)phenoxy)-9H-carbazole

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
105 °C

Procedure

2-(3-(4-Phenyl-1H-pyrazol-1-yl)phenoxy)-9H-carbazole 6 (401 mg, 1.0 mmol, 1.0 eq), Pd2(dba)3 (46 mg, 0.05 mmol, 0.05 eq), JohnPhos (30 mg, 0.10 mmol, 0.1 eq) and tBuONa (154 mg, 1.6 mmol, 1.6 eq) were added to a dry pressure Schlenk tube equipped with a magnetic stir bar. The tube was evacuated and back-filled with nitrogen, the evacuation and back-fill procedure was repeated twice. Then dry solvent toluene (4 mL), dioxane (4 mL) and 2-bromo-4-tert-butylpyridine (418 mg, 2.0 mmol, 2.0 eq) were added under a nitrogen atmosphere. The tube was sealed and the mixture was stirred at a temperature of 100-110° C. for 39 hours, and cooled to ambient temperature. The solvent was removed under reduced pressure and the residue was purified through column chromatography on silica gel using hexane and ethyl acetate (20:1-15:1-10:1-5:1) as an eluent to obtain the desired product, 9-(4-tert-butylpyridin-2-yl)-2-(3-(4-phenyl-1H-pyrazol-1-yl)phenoxy)-9H-carbazole Ligand ON6-tBu, as a brown solid (460 mg in 86% yield). 1H NMR (DMSO-d6, 400 MHz): δ 1.24 (s, 9H), 7.04 (dd, J=8.0, 2.6 Hz, 1H), 7.16 (dd, J=8.4, 2.4 Hz, 1H), 7.24 (t, J=7.6 Hz, 1H), 7.32-7.47 (m, 6H), 7.53 (t, J=8.4 Hz, 1H), 7.62 (d, J=1.2 Hz, 1H), 7.66 (t, J=2.0 Hz, 1H), 7.69-7.72 (m, 3H), 7.78 (d, J=8.4 Hz, 1H), 8.19 (s, 1H), 8.24 (d, J=7.6 Hz, 1H), 8.31 (d, J=8.8 Hz, 1H), 8.57 (d, J=5.6 Hz, 1H), 9.05 (s, 1H).

Workup

  1. customequipped with a magnetic stir bar
  2. customThe tube was evacuated
  3. additionback-filled with nitrogen
  4. customThe tube was sealed
  5. temperaturecooled to ambient temperature
  6. customThe solvent was removed under reduced pressure
  7. customthe residue was purified through column chromatography on silica gel

Sources & evidence

ORD record
ord-b549f31b3cfe4cda93521a0dc71371dd
Source dataset
uspto-grants-2015_12
Patent number
US09224963B2

Reaction notes

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