2-Cyclopenten-1-one → (R)-3-(4-Bromophenyl)cyclopentan-1-one

HRID 2276830Notes

Reaction equation

HRID 2276830 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5](OB(O)O)=[CH:4][CH:3]=1.[C:12]1(=[O:17])[CH2:16][CH2:15][CH:14]=[CH:13]1.C(=O)(O)[O-].[Na+]>O1CCOCC1.O.C/C(/O)=C/C(C)=O.C=C.C=C.[Rh].C1C=CC(P(C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C@@H:14]2[CH2:15][CH2:16][C:12](=[O:17])[CH2:13]2)=[CH:4][CH:3]=1

Participants

8

Reactant 3

HCID 135882-Cyclopenten-1-oneHCID 3155134-Bromophenyl-boric acidHCID 516892Sodium Bicarbonate

Product 1

HCID 49833221(R)-3-(4-Bromophenyl)cyclopentan-1-oneYield 93.6%

Reagents, catalysts & solvents 4

HCID 634876Binap, (A+-)-CatalystHCID 11010647ethene;(Z)-4-hydroxypent-3-en-2-one;rhodiumCatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Procedure

Under nitrogen stream, 4-bromophenylboric acid (15.7 g, 78 mmol), (R)-BINAP 1.17 g (1.9 mmol), and acetylacetonato bis(ethylene)rhodium(I) (486 mg, 1.9 mmol) were dissolved in a solvent mixture of 1,4-dioxane (150 mL) and water (15 mL), followed by degassing with ultrasonic waves. Subsequently, cyclopentenone (2.6 mL, 31 mmol) was added and the mixture was stirred under reflux with heating for 3 hours. The reaction solution was cooled to room temperature, followed by addition of saturated aqueous sodium bicarbonate solution, and then the solvent was distilled off under reduced pressure. The aqueous phase was extracted with ethyl acetate. The extracted solution was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue obtained was purified by column chromatography (ethyl acetate/hexane:20/80-30/70) to give the title compound (6.94 g, 91%).

Workup

  1. customby degassing with ultrasonic waves
  2. temperatureunder reflux
  3. temperaturewith heating for 3 hours
  4. distillationthe solvent was distilled off under reduced pressure
  5. extractionThe aqueous phase was extracted with ethyl acetate
  6. dry with materialThe extracted solution was dried over anhydrous magnesium sulfate
  7. distillationthe solvent was distilled off under reduced pressure
  8. customThe residue obtained
  9. customwas purified by column chromatography (ethyl acetate/hexane:20/80-30/70)

Sources & evidence

ORD record
ord-9f9ce91c620946b0aa6e028fec8bdac5
Source dataset
uspto-grants-2015_09
Patent number
US09133140B2

Reaction notes

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