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

HRID 1509633
Notes
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Reaction equation

HRID 1509633 reaction equation
[C:1]1([C:7]2[CH:12]=[CH:11][N:10]=[C:9]([C:13]3[CH:25]=[CH:24][C:23]4[C:22]5[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=5)[NH:16][C:15]=4[CH:14]=3)[CH:8]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Br[C:27]1[CH:39]=[CH:38][C:37]2[C:36]3[C:31](=[CH:32][CH:33]=[CH:34][CH:35]=3)[N:30]([C:40]3[CH:45]=[C:44]([C:46]([CH3:49])([CH3:48])[CH3:47])[CH:43]=[CH:42][N:41]=3)[C:29]=2[CH:28]=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:46]([C:44]1[CH:43]=[CH:42][N:41]=[C:40]([N:30]2[C:29]3[CH:28]=[C:27]([N:16]4[C:15]5[CH:14]=[C:13]([C:9]6[CH:8]=[C:7]([C:1]7[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=7)[CH:12]=[CH:11][N:10]=6)[CH:25]=[CH:24][C:23]=5[C:22]5[C:17]4=[CH:18][CH:19]=[CH:20][CH:21]=5)[CH:39]=[CH:38][C:37]=3[C:36]3[C:31]2=[CH:32][CH:33]=[CH:34][CH:35]=3)[CH:45]=1)([CH3:49])([CH3:47])[CH3:48]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 4

HCID 27342152-(Di-tert-butylphosphino)biphenylHCID 23676156Sodium t-butoxideHCID 1180072932-Bromo-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazoleHCID 1181139652-(4-phenylpyridin-2-yl)-9H-carbazole

Product 1

HCID 1181141049-(4-tert-butylpyridin-2-yl)-2'-(4-phenylpyridin-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-(4-phenylpyridin-2-yl)-9H-carbazole (676 mg, 2.11 mmol, 1.0 eq), 2-bromo-9-(4-tert-butylpyridin-2-yl)-9H-carbazole (958 mg, 2.53 mmol, 1.2 eq), Pd2(dba)3 (77 mg, 0.084 mmol, 0.04 eq), JohnPhos (50 mg, 0.169 mmol, 0.08 eq) and tBuONa (324 mg, 3.38 mmol, 1.6 eq). Then the tube was evacuated and back-filled with nitrogen, and the evacuation and back-fill procedure was repeated twice. Then dry solvent toluene (10 mL), dioxane (10 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 43 hours. 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 (10:1-8:1-5:1) as an eluent to obtain the desired product, 9-(4-tert-butylpyridin-2-yl)-2′-(4-phenylpyridin-2-yl)-9H-2,9′-bicarbazole Ligand N3NPh-ptb, as a brown solid (1175 mg in 90% yield). 1H NMR (DMSO-d6, 400 MHz): δ 1.15 (s, 9H), 7.25 (t, J=8.0 Hz, 1H), 7.31 (dd, J=5.2, 1.6 Hz, 1H), 7.34-7.57 (m, 9H), 7.74 (s, 1H), 7.78-7.82 (m, 3H), 7.91 (d, J=1.6 Hz, 1H), 8.11 (d, J=8.4 Hz, 1H), 8.21 (s, 1H), 8.24 (d, J=8.0 Hz, 1H), 8.29 (s, 1H), 8.31 (d, J=8.4 Hz, 2H), 8.45 (d, J=6.0 Hz, 1H), 8.51 (d, J=8.0 Hz, 1H), 8.57 (d, J=4.2 Hz, 1H). 13C NMR (DMSO-d6, 100 MHz): δ 29.96, 34.72, 108.01, 109.82, 109.85, 111.36, 115.97, 117.92, 119.14, 119.31, 119.80, 119.92, 120.23, 120.72, 120.84, 121.29, 122.00, 122.39, 122.94, 123.02, 123.45, 126.63, 126.84, 127.05, 129.06, 129.16, 134.83, 136.92, 137.49, 139.73, 139.78, 141.13, 141.47, 148.33, 149.39, 149.97, 150.55, 157.15, 163.08.

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 (10 mL), dioxane (10 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-0871e05e1c104faaae3e6fe6c9340047
Source dataset
uspto-grants-2015_12
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US09224963B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes