(3-Methoxyphenyl)boronic acid → HCID 59504489, compound

HRID 418914Notes

Reaction equation

HRID 418914 reaction equation
I[C:2]1[C:3](=[O:10])[CH2:4][CH2:5][C:6]([CH3:9])([CH3:8])[CH:7]=1.[CH3:11][O:12][C:13]1[CH:14]=[C:15](B(O)O)[CH:16]=[CH:17][CH:18]=1>O1CCCC1.O.[Ag]=O.C1C=CC(C#N)=CC=1.C1C=CC(C#N)=CC=1.Cl[Pd]Cl.C1([As](C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:11][O:12][C:13]1[CH:18]=[C:17]([C:2]2[C:3](=[O:10])[CH2:4][CH2:5][C:6]([CH3:9])([CH3:8])[CH:7]=2)[CH:16]=[CH:15][CH:14]=1

Participants

8

Reactant 2

HCID 2734370(3-Methoxyphenyl)boronic acidHCID 9992273HCID 9992273, compound

Product 1

HCID 59504489HCID 59504489, compoundYield 99.7%

Reagents, catalysts & solvents 5

HCID 11773TriphenylarsineCatalystHCID 92152Silver(II) oxideCatalystHCID 498840Bis(benzonitrile)palladium chlorideCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

Dissolve 2-iodo-4,4-dimethyl-cyclohex-2-enone(Tetrahedron Letters (1994), 35(37), 6787-90) (11 g, 44 mmol) in tetrahydrofuran (200 ml). Add 3-methoxyphenyl boronic acid (10 g, 65.8 mmol), triphenyl arsine (808 mg, 2.64 mmol), silver oxide (15.3 g, 66 mmol) in water (25 ml), bis(benzonitrile)dichloropalladium(II) (506 mg, 1.32 mmol). Stir at room temperature for 1 h. Quench with saturated aqueous ammonium chloride (200 ml), and stir 1 h. Filter reaction mixture through a bed of celite rinsing celite with ether (200 ml). Separate filtrate layers and extract the aqueous layer with additional ether (200 ml), combine organic extracts, and wash with water 2×(200 ml), brine (100 ml), dry, and concentrate. Chromatograph residue on a Biotage eluting with 10% ethyl acetate in hexanes to give (10.1 g, 99%) of the title compound as a yellow oil: 1H NMR (CDCl3) δ 7.26-7.23 (m, 1H), 6.88-6.84 (m, 3H), 6.69 (s, 1H), 3.81 (s, 3H), 2.62 (t, 2H), 1.96 (t, 2H), 1.25 (s, 6H).

Workup

  1. customQuench with saturated aqueous ammonium chloride (200 ml)
  2. stirringstir 1 h
  3. filtrationFilter
  4. customreaction mixture through a bed of celite rinsing celite with ether (200 ml)
  5. extractionSeparate filtrate layers and extract the aqueous layer with additional ether (200 ml)
  6. washwash with water 2×(200 ml), brine (100 ml)
  7. customdry
  8. concentrationconcentrate
  9. washChromatograph residue on a Biotage eluting with 10% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-dba963074c52417db682dd063f1d4968
Source dataset
uspto-grants-2012_01
Patent number
US08093302B2

Reaction notes

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