p-Bromoacetophenone → HCID 53817625, compound

HRID 1635567Notes

Reaction equation

HRID 1635567 reaction equation
B1C2CCCC1CCC2.[CH2:10]=[CH:11][CH2:12][CH2:13][CH3:14].[CH3:15][C:16]([C:18]1[CH:23]=[CH:22][C:21](Br)=[CH:20][CH:19]=1)=[O:17]>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:10][CH2:11][CH2:12][CH:13]([CH2:15][C:16]([C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)=[O:17])[CH3:14]

Participants

6

Reactant 3

HCID 7466p-BromoacetophenoneHCID 80041-PenteneHCID 789669-Borabicyclo(3.3.1)nonane

Product 1

HCID 53817625HCID 53817625, compoundYield 72%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Procedure

To a solution of 9-BBN (0.5 M in THF) (90.0 ml, 45.0 mmol) at 23° C., 1-pentene (4.93 ml, 45.0 mmol) was added. After 12 h, the solution was diluted with anhydrous dioxane (150 ml) and then 4-bromoacetophenone (5.97 g, 30.0 mmol) K3PO4 (9.55 g, 45.0 mmol), Pd(PPh3)4 (0.867 g, 0.750 mmol) were added. After deoxygenating the solution with N2 for 20 min, the solution was refluxed for 12 h. After cooling to ambient temperature, 3N NaOH (40 ml) and 30% H2O2 (40 ml) were added dropwise followed by dilution with hexanes (200 ml). After separation of layers, the organic layer was washed with brine (200 ml), dried, and concentrated under reduced pressure. The crude product was purified by flash chromatography eluting with 10% EtOAc/hexanes, to afford 4.09 g of 11 as an oil (72%). 1H NMR (CDCl3) δ 0.88 (t, J=6.9 Hz, 3H), 1.23-1.36 (m, 4H), 1.55-1.69 (m, 2H), 2.58 (s, 3 H), 2.66 (t, J=7.7 Hz, 2H), 7.25 (d, J=1.9 Hz, 2H), 7.86 (d, J=1.9 Hz, 2H); 13C NMR (CDCl3) δ 14.09, 22.58, 26.65, 30.89, 31.51, 36.04, 128.55, 128.68, 134.97, 148.92, 197.98.

Workup

  1. customAfter deoxygenating the solution with N2 for 20 min
  2. temperaturethe solution was refluxed for 12 h
  3. addition3N NaOH (40 ml) and 30% H2O2 (40 ml) were added dropwise
  4. customAfter separation of layers
  5. washthe organic layer was washed with brine (200 ml)
  6. customdried
  7. concentrationconcentrated under reduced pressure
  8. customThe crude product was purified by flash chromatography
  9. washeluting with 10% EtOAc/hexanes

Sources & evidence

ORD record
ord-9b2e16670e114fe2b270e6dc3766b3f9
Source dataset
uspto-grants-2003_01
Patent number
US06509367B1

Reaction notes

Loading…