proline dl-form → 3-allyltetrahydro-4H-pyran-4-one

HRID 73633

Reaction equation

HRID 73633 reaction equation
[O:1]1[CH2:6][CH2:5][C:4](=[O:7])[CH2:3][CH2:2]1.[CH2:8](O)[CH:9]=[CH2:10].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.N1CCCC1C(O)=O>CS(C)=O.[CH2-]C=C.[CH2-]C=C.Cl[Pd+].Cl[Pd+]>[CH2:10]([CH:3]1[C:4](=[O:7])[CH2:5][CH2:6][O:1][CH2:2]1)[CH:9]=[CH2:8]

Participants

7

Reactant 4

HCID 614proline dl-formHCID 7858Allyl AlcoholHCID 121599Tetrahydro-4H-pyran-4-oneHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)

Product 1

HCID 210779083-allyltetrahydro-4H-pyran-4-one

Reagents, catalysts & solvents 2

HCID 61538Palladium, di-mu-chlorobis(eta3-2-propenyl)di-CatalystHCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
70 °C

Procedure

A mixture of tetrahydro-4H-pyran-4-one (6-1) (5.17 g, 51.7 mmol), prop-2-en-1-ol (1.00 g, 17.2 mmol), allylPalladium Chloride dimer (0.157 g, 0.430 mmol), Xantphos (0.498 g, 0.861 mmol), and DL-proline (0.595 g, 5.17 mmol) in DMSO (35 mL) was degassed (2×pump/N2) and heated to 70° C. overnight. The mixture was cooled to rt and partitioned between water and Et2O. Extracted with Et2O. The combined organics were washed with 1:1 brine:water, dried (anhd. Na2SO4), filtered, and concentrated. The residue was purified by column chromatography to give the title compound. 1H NMR (500 MHz, CDCl3) δ 5.70-5.80 (m, 1H), 5.01-5.09 (m, 2H), 4.13-4.22 (m, 2H), 3.72-3.79 (m, 1H), 3.43 (t, 1H, J=11.2 Hz), 2.52-2.66 (m, 3H), 2.39-2.47 (m, 1H), 1.99-2.07 (m, 1H).

Workup

  1. customwas degassed (2×pump/N2)
  2. temperatureThe mixture was cooled to rt
  3. custompartitioned between water and Et2O
  4. extractionExtracted with Et2O
  5. washThe combined organics were washed with 1:1 brine
  6. dry with materialwater, dried (anhd. Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified by column chromatography

Sources & evidence

ORD record
ord-a0097975223e4495a57662e38607861e
Source dataset
uspto-grants-2014_09
Patent number
US08829196B2

Linked notes

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