Toluene → HCID 71007966, compound

HRID 2369734Notes

Reaction equation

HRID 2369734 reaction equation
Br[C:2]1[C:3]([CH3:21])=[CH:4][C:5]([C:8]2[C:13]3[O:14][C:15]4[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=4[C:12]=3[CH:11]=[CH:10][CH:9]=2)=[N:6][CH:7]=1.O.P([O-])([O-])([O-])=O.[K+].[K+].[K+].[C:31]1(C)C=CC=CC=1.CB1OB(C)OB(C)O1>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].C1(P(C2CCCCC2)C2C=CC=CC=2C2C(OC)=CC=CC=2OC)CCCCC1.O>[CH:11]1[C:12]2[C:16]3[CH:17]=[CH:18][CH:19]=[CH:20][C:15]=3[O:14][C:13]=2[C:8]([C:5]2[CH:4]=[C:3]([CH3:21])[C:2]([CH3:31])=[CH:7][N:6]=2)=[CH:9][CH:10]=1

Participants

8

Reactant 4

HCID 1140TolueneHCID 574072TrimethylboroxineHCID 22031701Potassium phosphate, tribasic, monohydrateHCID 71007915HCID 71007915, compound

Product 1

HCID 71007966HCID 71007966, compound

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylCatalystHCID 962WaterSolvent

Procedure

5-Bromo-2-(dibenzo[b,d]furan-4-yl)-4-methylpyridine (28.7 g, 85 mmol), dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine (1.394 g, 3.39 mmol) and potassium phosphate monohydrate (58.6 g, 255 mmol) were added to toluene (500 mL) and water (50 mL) and degassed for 20 min. Trimethylboroxine (14.83 mL, 106 mmol) and Pd2(dba)3 (0.777 g, 0.849 mmol) were added and the reaction mixture heated to reflux overnight. After cooling, the organic layer was separated and the aqueous layer extracted 3×50 mL with EtOAc, dried over sodium sulfate and evaporated. The crude product was chromatographed on silica gel with 8/2 (v/v) dichloromethane/EtOAc in hexane to give 19.2 g of an off-white solid, which was recrystallized from hexane to give 16.8 g (83%) of the product as white needles. The product was confirmed by NMR and HPLC (99.97% pure).

Workup

  1. customdegassed for 20 min
  2. temperaturethe reaction mixture heated
  3. temperatureto reflux overnight
  4. temperatureAfter cooling
  5. customthe organic layer was separated
  6. extractionthe aqueous layer extracted 3×50 mL with EtOAc
  7. dry with materialdried over sodium sulfate
  8. customevaporated
  9. customThe crude product was chromatographed on silica gel with 8/2 (v/v) dichloromethane/EtOAc in hexane

Sources & evidence

ORD record
ord-5a222bf920e648b6a7470aa12716a193
Source dataset
uspto-grants-2014_04
Patent number
US08709615B2

Reaction notes

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