2-(Di-tert-butylphosphino)biphenyl → 9-(4-phenylpyridin-2-yl)-2'-(pyridin-2-yl)-9H-2,9'-bicarbazole

HRID 1509636Notes

Reaction equation

HRID 1509636 reaction equation
[N:1]1[CH:6]=[CH:5][CH:4]=[CH:3][C:2]=1[C:7]1[CH:19]=[CH:18][C:17]2[C:16]3[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=3)[N:10]([C:20]3[CH:32]=[CH:31][C:30]4[C:29]5[C:24](=[CH:25][CH:26]=[CH:27][CH:28]=5)[NH:23][C:22]=4[CH:21]=3)[C:9]=2[CH:8]=1.Cl[C:34]1[CH:39]=[C:38]([C:40]2[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=2)[CH:37]=[CH:36][N:35]=1.CC(P(C(C)(C)C)C1C(C2C=CC=CC=2)=CC=CC=1)(C)C.CC([O-])(C)C.[Na+]>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]>[C:40]1([C:38]2[CH:39]=[CH:34][N:35]=[C:36]([N:23]3[C:22]4[CH:21]=[C:20]([N:10]5[C:9]6[CH:8]=[C:7]([C:2]7[CH:3]=[CH:4][CH:5]=[CH:6][N:1]=7)[CH:19]=[CH:18][C:17]=6[C:16]6[C:11]5=[CH:12][CH:13]=[CH:14][CH:15]=6)[CH:32]=[CH:31][C:30]=4[C:29]4[C:24]3=[CH:25][CH:26]=[CH:27][CH:28]=4)[CH:37]=2)[CH:41]=[CH:42][CH:43]=[CH:44][CH:45]=1

Participants

6

Reactant 4

HCID 27342152-(Di-tert-butylphosphino)biphenylHCID 27628422-Chloro-4-phenylpyridineHCID 23676156Sodium t-butoxideHCID 1181139882'-(pyridin-2-yl)-9H-2,9'-bicarbazole

Product 1

HCID 1181139789-(4-phenylpyridin-2-yl)-2'-(pyridin-2-yl)-9H-2,9'-bicarbazole

Reagents, catalysts & solvents 1

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Conditions

Temperature
100 °C

Procedure

To a dry pressure Schlenk tube equipped with a magnetic stir bar was added 2′-(pyridin-2-yl)-9H-2,9′-bicarbazole (409 mg, 1.0 mmol, 1.0 eq), 2-chloro-4-phenylpyridine (228 mg, 1.2 mmol, 1.2 eq), Pd2(dba)3 (36 mg, 0.04 mmol, 0.04 eq), JohnPhos (48 mg, 0.16 mmol, 0.16 eq) and tBuONa (154 mg, 1.6 mmol, 1.6 eq). Then the tube was evacuated and back-filled with nitrogen, the evacuation and back-fill procedure was repeated twice. Then dry solvent toluene (4 mL) and dioxane (4 mL) were added under the protection of nitrogen. The tube was sealed and the mixture was stirred in an oil bath at a temperature of 95-105° C. for 2 days. Then the mixture was 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 (10:1-5:1-3:1) as an eluent to obtain the desired product, 9-(4-phenylpyridin-2-yl)-2′-(pyridin-2-yl)-9H-2,9′-bicarbazole Ligand N3NPh, as a brown solid (561 mg in 99.7% yield). 1H NMR (DMSO-d6, 400 MHz): δ 7.29-7.34 (m, 2H), 7.41-7.48 (m, 5H), 7.53-7.60 (m, 2H), 7.64 (dd, J=8.0, 1.2 Hz, 1H), 7.76 (d, J=4.8 Hz, 1H), 7.82-7.88 (m, 3H), 7.97 (d, J=8.0 Hz, 1H), 8.05 (d, J=8.4 Hz, 1H), 8.10 (s, 1H), 8.19 (s, 1H), 8.26 (s, 1H), 8.30 (d, J=7.6 Hz, 1H), 8.36 (d, J=8.4 Hz, 1H), 8.42 (d, J=8.0 Hz, 1H), 8.59-8.61 (m, 2H), 8.70 (d, J=5.6 Hz, 1H). 13C NMR (DMSO-d6, 100 MHz): δ 107.61, 109.87, 110.25, 111.57, 116.34, 118.65, 119.76, 119.97, 120.25, 120.35, 120.77, 120.81, 120.88, 121.48, 122.05, 122.39, 122.42, 123.07, 123.13, 123.38, 126.70, 126.98, 127.09, 129.16, 129.66, 134.83, 136.48, 136.74, 137.22, 139.79, 139.80, 141.25, 141.50, 149.46, 150.17, 150.40, 151.30, 156.16.

Workup

  1. customTo a dry pressure Schlenk tube equipped with a magnetic stir bar
  2. customThen the tube was evacuated
  3. additionback-filled with nitrogen
  4. additionThen dry solvent toluene (4 mL) and dioxane (4 mL) were added under the protection of nitrogen
  5. customThe tube was sealed
  6. temperatureThen the mixture was cooled to ambient temperature
  7. customThe solvent was removed under reduced pressure
  8. customthe residue was purified through column chromatography on silica gel

Sources & evidence

ORD record
ord-63f50f197b9c4774beaa65e110b43de8
Source dataset
uspto-grants-2015_12
Patent number
US09224963B2

Reaction notes

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