Toluene → 2-([1,1'-Biphenyl]-3-yl)-4,5-dimethylpyridine

HRID 2400236Notes

Reaction equation

HRID 2400236 reaction equation
[C:1]1([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[CH:6]=[CH:5][CH:4]=[C:3]([C:7]2[CH:12]=[C:11]([CH3:13])[C:10](Br)=[CH:9][N:8]=2)[CH:2]=1.[CH3:21]B1OB(C)OB(C)O1.O.[O-]P([O-])([O-])=O.[K+].[K+].[K+].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].C1(P(C2CCCCC2)C2C=C(C3C(OC)=CC=CC=3OC)C=CC=2)CCCCC1.O>[C:1]1([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[CH:6]=[CH:5][CH:4]=[C:3]([C:7]2[CH:12]=[C:11]([CH3:13])[C:10]([CH3:21])=[CH:9][N:8]=2)[CH:2]=1

Participants

8

Reactant 4

HCID 1140TolueneHCID 574072TrimethylboroxineHCID 22031701Potassium phosphate, tribasic, monohydrateHCID 710081052-([1,1'-Biphenyl]-3-yl)-5-bromo-4-methylpyridine

Product 1

HCID 592948462-([1,1'-Biphenyl]-3-yl)-4,5-dimethylpyridineYield 87%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 58401078Dicyclohexyl(2',6'-dimethoxybiphenyl-3-yl)phosphineCatalystHCID 962WaterSolvent

Procedure

2-([1,1′-Biphenyl]-3-yl)-5-bromo-4-methylpyridine 11.5 g (35.5 mmol), 2,4,6-trimethyl-1,3,5,2,4,6-trioxatriborinane (5.57 g, 44.3 mmol), dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-3-yl)phosphine (1.2 g, 2.84 mmol), Pd2dba3 (0.650 g, 0.709 mmol) and potassium phosphate tribasic monohydrate, 250 mL toluene and 25 mL of water were placed in flask under nitrogen. The reaction mixture was degassed with nitrogen for 20 minutes and heated to reflux for 24 h. After cooling, the organic layer was separated and the aqueous layer extracted 3×50 mL with dichloromethane, dried over sodium sulfate and evaporated. The crude product was chromatographed on silica gel with 5% dichloromethane in hexane to give 8.0 g (87%) of the product. The product was confirmed by NMR and GC/MS.

Workup

  1. customThe reaction mixture was degassed with nitrogen for 20 minutes
  2. temperatureheated
  3. temperatureto reflux for 24 h
  4. temperatureAfter cooling
  5. customthe organic layer was separated
  6. extractionthe aqueous layer extracted 3×50 mL with dichloromethane
  7. dry with materialdried over sodium sulfate
  8. customevaporated
  9. customThe crude product was chromatographed on silica gel with 5% dichloromethane in hexane

Sources & evidence

ORD record
ord-159c40f7b7d946e198d822c08393aa61
Source dataset
uspto-grants-2014_08
Patent number
US08795850B2

Reaction notes

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