Water → (S)-3-(4-Bromophenyl)cyclopentan-1-one

HRID 2421500Notes

Reaction equation

HRID 2421500 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5](B(O)O)=[CH:4][CH:3]=1.O.[C:12]1(=[O:17])[CH2:16][CH2:15][CH:14]=[CH:13]1>O1CCOCC1>[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

5

Reactant 3

HCID 962WaterHCID 135882-Cyclopenten-1-oneHCID 79599(4-Bromophenyl)boronic acid

Product 1

HCID 25002103(S)-3-(4-Bromophenyl)cyclopentan-1-oneYield 89%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Conditions

Temperature
35 °C

Procedure

Alternatively, a 3 L three-necked round-bottomed flask equipped with a temperature probe and a nitrogen bubbler was charged with 4-bromophenylboronic acid (100 g, 498 mmol) and hydroxy[(S)-BINAP]rhodium(I) dimer (6.20 g, 4.17 mmol) in dioxane (1667 mL) and water (167 mL) at room temperature. The resulting suspension was degassed with nitrogen and 2-cyclopenten-1-one (27.8 mL, 332 mmol) was added in one portion. The mixture was further degassed for 5 minutes and heated at 35° C. for about 16 hours. The reaction mixture was cooled to room temperature and concentrated. The brown residue was treated with EtOAc (500 mL) and filtered. The filtrate was washed with a saturated solution of NaHCO3 (500 mL) and brine (500 mL), dried over MgSO4, filtered, and concentrated to afford a dark brown solid. The crude reaction product was purified by silica gel chromatography (1:9 EtOAc:heptane as eluant). Fractions containing product were combined and concentrated to afford (S)-3-(4-bromo-phenyl)-cyclopentanone (70.4 g, 89%, 95% ee as determined by chiral HPLC) as an ivory solid.

Workup

  1. customAlternatively, a 3 L three-necked round-bottomed flask equipped with a temperature probe
  2. customat room temperature
  3. additionwas added in one portion
  4. customThe mixture was further degassed for 5 minutes
  5. temperatureThe reaction mixture was cooled to room temperature
  6. concentrationconcentrated
  7. additionThe brown residue was treated with EtOAc (500 mL)
  8. filtrationfiltered
  9. washThe filtrate was washed with a saturated solution of NaHCO3 (500 mL) and brine (500 mL)
  10. dry with materialdried over MgSO4
  11. filtrationfiltered
  12. concentrationconcentrated
  13. customto afford a dark brown solid
  14. customThe crude reaction product
  15. customwas purified by silica gel chromatography (1:9 EtOAc:heptane as eluant)
  16. additionFractions containing product
  17. concentrationconcentrated

Sources & evidence

ORD record
ord-90d4c859d59e4dd3a94d7f0f5e10b872
Source dataset
uspto-grants-2011_06
Patent number
US07956195B2

Reaction notes

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