2-Cyclohexen-1-one → 3-Phenylcyclohexanone

HRID 1021518Notes

Reaction equation

HRID 1021518 reaction equation
[C:1]1(B(O)O)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.O1CCOCC1.O.[C:17]1(=[O:23])[CH2:22][CH2:21][CH2:20][CH:19]=[CH:18]1>CCOC(C)=O.C/C(/O)=C/C(C)=O.C=C.C=C.[Rh].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:1]1([CH:19]2[CH2:20][CH2:21][CH2:22][C:17](=[O:23])[CH2:18]2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

7

Reactant 3

HCID 135942-Cyclohexen-1-oneHCID 66827Phenylboronic AcidHCID 218864351,4-Dioxane--water (1/1)

Product 1

HCID 2736613-PhenylcyclohexanoneYield 33.4%

Reagents, catalysts & solvents 3

HCID 634876Binap, (A+-)-CatalystHCID 11010647ethene;(Z)-4-hydroxypent-3-en-2-one;rhodiumCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
120 °C

Procedure

To a solution of phenylboronic acid (0.630 g, 5.17 mmol) and 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (0.0193 g, 0.0310 mmol) in 10:1 dioxane/water (2.5 ml) was added acetylacetonatobis(ethylene)rhodium(I) (0.00800 g, 0.0310 mmol), and the reaction was degassed with argon. To this was added cyclohex-2-enone (0.100 ml, 1.03 mmol), and the reaction was heated to 120° C. for 16 hours in a screw-top vial. The reaction was allowed to cool to ambient temperature, diluted with EtOAc, and washed with twice with saturated sodium bicarbonate and once with saturated sodium chloride. The organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated. The crude material was purified on a Biotage SP1 system eluting with a linear gradient of 5-50% EtOAc in hexanes to yield 60 mg of the title compound (33.3% yield).

Workup

  1. customthe reaction was degassed with argon
  2. temperatureto cool to ambient temperature
  3. washwashed with twice with saturated sodium bicarbonate
  4. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude material was purified on a Biotage SP1 system
  8. washeluting with a linear gradient of 5-50% EtOAc in hexanes

Sources & evidence

ORD record
ord-504e0fdcfc23455189d463f683eca304
Source dataset
uspto-grants-2014_05
Patent number
US08716498B2

Reaction notes

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