Allyl acetate → 2-Allyl-2-phenylcyclohexanone

HRID 714248Notes

Reaction equation

HRID 714248 reaction equation
[C:1]1([CH:7]2[CH2:12][CH2:11][CH2:10][CH2:9][C:8]2=[O:13])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C[Si]([N-][Si](C)(C)C)(C)C.[Na+].C(O[CH2:28][CH:29]=[CH2:30])(=O)C>COCCOC.[CH2-]C=C.[CH2-]C=C.Cl[Pd+].Cl[Pd+].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH2:30]([C:7]1([C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[CH2:12][CH2:11][CH2:10][CH2:9][C:8]1=[O:13])[CH:29]=[CH2:28]

Participants

7

Reactant 3

HCID 11584Allyl acetateHCID 955922-PhenylcyclohexanoneHCID 2724254Sodium bis(trimethylsilyl)amide

Product 1

HCID 130232142-Allyl-2-phenylcyclohexanoneYield 91%

Reagents, catalysts & solvents 3

HCID 11776TriphenylphosphineCatalystHCID 61538Palladium, di-mu-chlorobis(eta3-2-propenyl)di-CatalystHCID 80711,2-DimethoxyethaneSolvent2×

Procedure

To a solution of 2-phenylcyclohexanone (2 g, 11.48 mmol) in 50 ml of anhydrous DME in an ice bath was added 1M sodium bis(trimethylsilyl)amide (12.63 mL, 12.63 mmol) dropwise and the solution was stirred at the same temp for 20 minutes. In a separated flask allylpalladium chloride dimer (0.104 g, 0.287 mmol) was dissolved in 10 ml of anhydrous DME, and triphenylphosphine (0.151 g, 0.574 mmol) was added to the solution. It was stirred for 20 minutes at room temp and then allyl acetate (1.300 mL, 12.05 mmol) was added. This solution was added to the anion solution dropwise and the mixture was stirred at room temp for 2 hrs. The reaction was quenched with saturated NH4Cl and extracted with hexane. The organic layer was washed with brine. The combine aqueous layers were back-extracted with hexane once and combined. Dried over Na2SO4 and evaporated to give an oily residue. It was purified by Combiflash (120 g silica gel) eluting with hexane followed by 1:9 EtOAc-hexane to give 2.24 g of 2-allyl-2-phenylcyclohexanone. 1H NMR (400 MHz, CDCl3) δ ppm 7.35 (2 H, t, J=7.58 Hz), 7.21-7.27 (1 H, m), 7.12-7.18 (2 H, m), 5.35-5.52 (1 H, m), 4.82-4.97 (2 H, m), 2.61-2.72 (1 H, m), 2.39-2.55 (2 H, m), 2.24-2.38 (2 H, m), 1.89-1.99 (1 H, m, J=9.39, 6.15, 2.88, 2.88 Hz), 1.62-1.81 (4 H, m).

Workup

  1. stirringIt was stirred for 20 minutes at room temp
  2. additionThis solution was added to the anion solution dropwise
  3. stirringthe mixture was stirred at room temp for 2 hrs
  4. customThe reaction was quenched with saturated NH4Cl
  5. extractionextracted with hexane
  6. washThe organic layer was washed with brine
  7. extractionThe combine aqueous layers were back-extracted with hexane once
  8. dry with materialDried over Na2SO4
  9. customevaporated
  10. customto give an oily residue
  11. customIt was purified by Combiflash (120 g silica gel)
  12. washeluting with hexane

Sources & evidence

ORD record
ord-5236916bc362457b9a81b9abcc5267ee
Source dataset
uspto-grants-2015_11
Patent number
US09187437B2

Reaction notes

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