1,4-Dioxane → 1,1,1,3,3,3-Hexafluoro-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)propan-2-ol

HRID 2420920Notes

Reaction equation

HRID 2420920 reaction equation
[CH:1]1(P(C2CCCCC2)C2CCCCC2)[CH2:6]CCC[CH2:2]1.[C:20]([O-:23])(=O)[CH3:21].[K+].[O:25]1CCO[BH:26]1.Br[C:31]1[CH:36]=[CH:35][C:34]([C:37]([OH:46])([C:42]([F:45])([F:44])[F:43])[C:38]([F:41])([F:40])[F:39])=[CH:33][CH:32]=1.O1CCOC[CH2:48]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]>[F:39][C:38]([F:41])([F:40])[C:37]([C:34]1[CH:35]=[CH:36][C:31]([B:26]2[O:25][C:1]([CH3:6])([CH3:2])[C:20]([CH3:21])([CH3:48])[O:23]2)=[CH:32][CH:33]=1)([OH:46])[C:42]([F:45])([F:44])[F:43]

Participants

7

Reactant 5

HCID 312751,4-DioxaneHCID 75806TricyclohexylphosphineHCID 517044Potassium AcetateHCID 5326306InChI=1/C2H5BO2/c1-2-5-3-4-1/h3H,1-2HHCID 232335702-(4-Bromophenyl)-1,1,1,3,3,3-hexafluoropropan-2-ol

Product 1

HCID 591663151,1,1,3,3,3-Hexafluoro-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)propan-2-olYield 38%

Reagents, catalysts & solvents 1

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalyst

Conditions

Temperature
80 °C

Procedure

To a suspension of Pd(dba)2 (100 mg, 0.20 mmol) and PCy3 (130 mg, 0.50 mmol) in dioxane (8 mL) were added potassium acetate (920 mg, 9.4 mmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane (1.8 g, 7.1 mmol) and 2-(4-bromophenyl)-1,1,1,3,3,3-hexafluoropropan-2-ol (2.0 g, 6.2 mmol). The mixture was heated at 80° C. overnight. The mixture was quenched with H2O and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over MgSO4, and concentrated under reduced pressure. The residue was purified by column chromatography (0-5% ethyl acetate-petroleum ether) to afford 1,1,1,3,3,3-hexafluoro-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)propan-2-ol (870 mg, 38%). 1H NMR (CDCl3, 400 MHz) δ 7.89 (d, J=8.0 Hz, 2H), 7.71 (d, J=8.0 Hz, 2H), 3.50 (s, 1H), 1.35 (s, 12H).

Workup

  1. customThe mixture was quenched with H2O
  2. extractionthe aqueous layer was extracted with ethyl acetate
  3. washThe combined organic layers were washed with brine
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was purified by column chromatography (0-5% ethyl acetate-petroleum ether)

Sources & evidence

ORD record
ord-087dafde713e4c57849ec532c8c5b40e
Source dataset
uspto-grants-2011_06
Patent number
US07956052B2

Reaction notes

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