2-Chloroanisole → 2-Methoxy-4'-methyl-1,1'-biphenyl

HRID 1884184Notes

Reaction equation

HRID 1884184 reaction equation
Cl[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[O:8][CH3:9].[CH3:10][C:11]1[CH:16]=[CH:15][C:14](B(O)O)=[CH:13][CH:12]=1.[F-].[Cs+]>O1CCOCC1.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].N(P(Cl)Cl)(C1CCCCC1)C1CCCCC1>[CH3:10][C:11]1[CH:16]=[CH:15][C:14]([C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=2[O:8][CH3:9])=[CH:13][CH:12]=1

Participants

7

Reactant 3

HCID 130112-ChloroanisoleHCID 25953Cesium fluorideHCID 79799Tolylboronic acid

Product 1

HCID 103135412-Methoxy-4'-methyl-1,1'-biphenylYield 83.2%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 13311825Dichloro(dicyclohexylamino)phosphineCatalystHCID 312751,4-DioxaneSolvent

Procedure

The general procedure from Example 12 was followed using 2-chloro-anisole (143 mg, 1.0 mmol) and 4—MeC6H4B(OH)2 (204 mg, 1.5 mmol) with Pd2(dba)3 (13.3 mg, 0.0145 mmol) and (Me3C)2PH(O) from Experiment 2 (9.6 mg, 0.058 mmol) and CsF (456 mg, 3.0 mmol) in 4.0 mL of 1,4-dioxane. After 24 h, the reaction mixture was chromatographed with 5% ethyl acetate/hexane to give 165 mg (83% yield) of 2-(4-methylphenyl)anisole. It was >95% pure by 1H NMR and GC/MS. 1H NMR (500 MHz, CDCl3): δ7.32 (d, J=8.06 Hz, 2H), 7.18 (m, 2H), 7.10 (d, J=7.88 Hz, 2H), 6.92−6.84 (m, 2H), 3.67 (s, 3H), 2.28 (s, 3H) ppm. 13C NMR (125 MHz, CDCl3): δ156.5, 136.5, 135.6, 130.7, 129.4, 128.7, 128.3, 120.8, 111.2, 55.5, 21.1 ppm.

Workup

  1. customthe reaction mixture was chromatographed with 5% ethyl acetate/hexane

Sources & evidence

ORD record
ord-5daae16380e9446aa094142b779ae521
Source dataset
uspto-grants-2004_07
Patent number
US06762330B2

Reaction notes

Loading…