Phenylboronic Acid → 1-(2,6-Dihydroxy[1,1'-biphenyl]-3-yl)ethan-1-one

HRID 2267019Notes

Reaction equation

HRID 2267019 reaction equation
[OH:1][C:2]1[C:7](I)=[C:6]([OH:9])[CH:5]=[CH:4][C:3]=1[C:10](=[O:12])[CH3:11].[C:13]1(B(O)O)[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.O.[OH-].[Cs+]>O1CCCC1.O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[OH:1][C:2]1[C:3]([C:10](=[O:12])[CH3:11])=[CH:4][CH:5]=[C:6]([OH:9])[C:7]=1[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

6

Reactant 3

HCID 66827Phenylboronic AcidHCID 132755071-(2,4-Dihydroxy-3-iodophenyl)ethan-1-oneHCID 23679066Caesium hydroxide--water (1/1/1)

Product 1

HCID 573554611-(2,6-Dihydroxy[1,1'-biphenyl]-3-yl)ethan-1-one

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 21881883Oxolane--water (1/1)Solvent

Procedure

To a solution of 1-(2,4-dihydroxy-3-iodo-phenyl)-ethanone (1.0 g, 3.59 mmol; 581938, may be prepared as described in G. Batu and R. Stevenson, J. Org. Chem. 1979, 44, 3948) in tetrahydrofuran/water (15 mL/3 mL) at room temperature is added phenyl boronic acid (0.877 g, 7.19 mmol), Pd(dppf)2Cl2 (0.088 g, 0.107 mmol), and cesium hydroxide monohydrate (1.81 g, 10.8 mmol). After stirring for 15 hours, the mixture is filtered through a pad of Celite®, washing with ethyl acetate. The residue is diluted with 30 mL of 1N hydrochloric acid and extracted with ethyl acetate. The combined organic phases are washed with brine; dried over magnesium sulfate; filtered and concentrated under reduced pressure. The resulting residue is purified by flash chromatography, eluting with 30% ethyl acetate/hexanes to give the title compound as a colorless solid: MS (m/z) 228(M+); 1H NMR (DMSO-d6) δ 13.1 (s, 1H), 10.6 (bs, 1H), 7.81 (d, J=8.8 Hz, 1H), 7.41-7.28 (m, 5H), 6.61 (d, J=8.8 Hz, 1H), 2.58 (s, 3H); Rf=0.58 in 40% ethyl acetate/hexanes.

Workup

  1. filtrationthe mixture is filtered through a pad of Celite®
  2. washwashing with ethyl acetate
  3. additionThe residue is diluted with 30 mL of 1N hydrochloric acid
  4. extractionextracted with ethyl acetate
  5. washThe combined organic phases are washed with brine
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customThe resulting residue is purified by flash chromatography
  10. washeluting with 30% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-e7c642060e744aa0aa1794276641818d
Source dataset
uspto-grants-2010_12
Patent number
US07858646B2

Reaction notes

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