2-Cyclohexen-1-one → 3-[4-(1,1-Dimethylethyl)phenyl]cyclohexanone

HRID 2404373Notes

Reaction equation

HRID 2404373 reaction equation
[C:1]1(=[O:7])[CH2:6][CH2:5][CH2:4][CH:3]=[CH:2]1.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:54]([C:58]1[CH:63]=[CH:62][C:61](B(O)O)=[CH:60][CH:59]=1)([CH3:57])([CH3:56])[CH3:55]>C/C(/O)=C/C(C)=O.C=C.C=C.[Rh].O1CCOCC1.O>[C:54]([C:58]1[CH:63]=[CH:62][C:61]([CH:3]2[CH2:4][CH2:5][CH2:6][C:1](=[O:7])[CH2:2]2)=[CH:60][CH:59]=1)([CH3:57])([CH3:56])[CH3:55]

Participants

6

Reactant 3

HCID 135942-Cyclohexen-1-oneHCID 634876Binap, (A+-)-HCID 27343204-tert-Butylphenylboronic acid

Product 1

HCID 645209143-[4-(1,1-Dimethylethyl)phenyl]cyclohexanoneYield 61.1%

Reagents, catalysts & solvents 2

HCID 11010647ethene;(Z)-4-hydroxypent-3-en-2-one;rhodiumCatalystHCID 218864351,4-Dioxane--water (1/1)Solvent

Conditions

Temperature
100 °C

Procedure

To a 40 mL microwave flask containing 10/1 dioxane/H2O (22 mL) was added cyclohexen-1-one (1.35 g, 14.0 mmol), acetylacetonatobis(ethylene)rhodium(I) (0.36 g, 1.40 mmol), racemic 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (0.88 g, 1.40 mmol) and 4-tert-butylphenylboronic acid (5.0 g, 28.0 mmol). The reaction mixture was heated in the microwave at 100° C. for 20 minutes. The material was poured into a separatory funnel and extracted with ethyl acetate (150 mL), washed with saturated aqueous NaHCO3 (75 mL), dried (Na2SO4), filtered, and concentrated. The residue was purified by silica gel chromatography (20% EtOAc/hexanes) to afford the title compound (1.97 g, 61%) as a yellow oil. 1H NMR (CD3OD, 300 MHz) δ 1.30 (s, 9H), 1.68-2.17 (m, 4H), 2.32-2.38 (m, 3H), 2.64 (dt, J=1.01, 12.0 Hz, 1H), 2.91-3.01 (m, 1H), 7.11-7.20 (m, 2H), 7.31-7.36 (m, 2H); MS (DCI) m/z 248 (M+H)+.

Workup

  1. additionThe material was poured into a separatory funnel
  2. extractionextracted with ethyl acetate (150 mL)
  3. washwashed with saturated aqueous NaHCO3 (75 mL)
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe residue was purified by silica gel chromatography (20% EtOAc/hexanes)

Sources & evidence

ORD record
ord-21d60a7a81254c59987b23ea2640c7cf
Source dataset
uspto-grants-2014_08
Patent number
US08802711B2

Reaction notes

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