Oxygen → HCID 57691471, compound

HRID 1867639Notes

Reaction equation

HRID 1867639 reaction equation
[F:1][C:2]([F:28])([F:27])[C:3]1[CH:4]=[C:5]([CH:20]=[C:21]([C:23]([F:26])([F:25])[F:24])[CH:22]=1)[CH2:6][O:7][CH2:8][C:9]([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[CH2:18][OH:19])=[CH:10][CH3:11].N1C=CC=CC=1.C(=O)([O-])[O-].[Na+].[Na+].O=O.[BH4-].[Na+]>CCOCC.FC(F)(F)C([O-])=O.[Pd+2].FC(F)(F)C([O-])=O.C1(C)C=CC=CC=1>[F:1][C:2]([F:27])([F:28])[C:3]1[CH:4]=[C:5]([CH:20]=[C:21]([C:23]([F:24])([F:26])[F:25])[CH:22]=1)[CH2:6][O:7][CH2:8][C:9]1([CH:10]=[CH2:11])[C:12]2[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=2)[CH2:18][O:19]1

Participants

9

Reactant 5

HCID 977OxygenHCID 1049PyridineHCID 10340Sodium CarbonateHCID 4311764Sodium borohydrideHCID 76594466HCID 76594466, compound

Product 1

HCID 57691471HCID 57691471, compound

Reagents, catalysts & solvents 3

HCID 2733347Palladium(II) trifluoroacetateCatalystHCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
80 °C

Procedure

A flask was charged with (2-(1-(3,5-bis(trifluoromethyl)benzyloxy)but-2-en-2-yl)phenyl)methanol (1.22 g, 3.0 mmol), palladium trifluoroacetate (50.2 mg, 0.15 mmol), pyridine (0.049 mL, 0.60 mmol), sodium carbonate (160 mg, 1.5 mmol), molecular sieves (3 A, 1.5 g), and toluene (16 mL). The mixture was stirred under a balloon of oxygen, and was heated at 80° C. for 3 h. The reaction was cooled to room temperature, diluted with ether, and filtered through celite. The organics were washed with water (2×), then brine, dried over magnesium sulfate, and concentrated. To aid in separation of the aldehyde byproduct (via oxidation of the alcohol), the following procedure was used to convert it back to starting material. The crude mixture was dissolved in ethanol (6 mL) and treated with sodium borohydride (30 mg, 0.79 mmol). The mixture was stirred at room temperature for 10 min. The mixture was cooled to 0° C., quenched by addition of saturated ammonium chloride, diluted with ether, washed with water (2×), then brine, dried over magnesium sulfate, and concentrated. Column chromatography (2.5%-->30% EtOAc/Hex) gave 828 mg (68%) as a colorless oil. 1H-NMR (CDCl3, 300 MHz) δ 7.79 (s, 1H), 7.70 (s, 2H), 7.33 (m, 2H), 7.25 (m, 2H), 6.17 (dd, J=17.1, 10.7 Hz, 1H), 5.44 (dd, J=17.1, 1.5 Hz, 1H), 5.24 (dd, J=10.7, 1.2 Hz, 1H), 5.20 (qAB, JAB=12.2 Hz, 2H), 4.70 (qAB, JAB=13.4 Hz, 2H), 3.83 (qAB, JAB=10.4 Hz, 2H); 13C-NMR (CDCl3, 126 MHz) δ 141.4, 141.0, 139.6, 138.2, 131.7 (q, J=33.6 Hz), 128.2, 127.5, 127.2, 123.5 (q, J=273 Hz), 121.9, 121.4, 121.3, 115.0, 90.1, 76.1, 72.4, 72.0. Mass spec.: 425.12 (MNa)+.

Workup

  1. temperatureThe reaction was cooled to room temperature
  2. filtrationfiltered through celite
  3. washThe organics were washed with water (2×)
  4. dry with materialbrine, dried over magnesium sulfate
  5. concentrationconcentrated
  6. customTo aid in separation of the aldehyde byproduct (via oxidation of the alcohol), the following procedure
  7. dissolutionThe crude mixture was dissolved in ethanol (6 mL)
  8. temperatureThe mixture was cooled to 0° C.
  9. customquenched by addition of saturated ammonium chloride
  10. additiondiluted with ether
  11. washwashed with water (2×)
  12. dry with materialbrine, dried over magnesium sulfate
  13. concentrationconcentrated
  14. customColumn chromatography (2.5%-->30% EtOAc/Hex) gave 828 mg (68%) as a colorless oil

Sources & evidence

ORD record
ord-dec9de2432c24b6ca53bfcc4a12c79eb
Source dataset
uspto-grants-2009_12
Patent number
US07632861B2

Reaction notes

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