Hydrochloric Acid → (+)-(S)-2-methyl-3-(pent-4-en-2-ynyl)-cyclopent-2-en-4-one-1-ol

HRID 483692Notes

Reaction equation

HRID 483692 reaction equation
[CH3:1][C:2]1[C@@H:3]([OH:11])[CH2:4][C:5](=[O:10])[C:6]=1[CH2:7][C:8]#[CH:9].[CH2:12](N(CC)CC)[CH3:13].C(Br)=C.Cl>C1C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:1][C:2]1[C@@H:3]([OH:11])[CH2:4][C:5](=[O:10])[C:6]=1[CH2:7][C:8]#[C:9][CH:12]=[CH2:13]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 8471TriethylamineHCID 11641BromoetheneHCID 1569974-Hydroxy-3-methyl-2-(prop-2-yn-1-yl)cyclopent-2-en-1-one

Product 1

HCID 11829962(+)-(S)-2-methyl-3-(pent-4-en-2-ynyl)-cyclopent-2-en-4-one-1-ol

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 241BenzeneSolvent

Procedure

10 Grams of (+)-(S)-2-methyl-3-propargylcyclopent-2-en-4-one-1-ol was dissolved in 100 ml of benzene. Thereto were added successively 3.85 g of tetrakis(triphenylphosphine)palladium, 1.27 g of cuprous iodide and 13.5 g of triethylamine. 150 Grams of vinyl bromide was promptly added to the resultant mixture. The mixture was stirred under nitrogen atmosphere at room temperature overnight. Thereafter, the mixture was poured on dilute hydrochloric acid. A benzene layer was recovered from the mixture, and the water layer was further extracted with benzene. The benzene layers were mixed, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure. Methanol was added to the residue, and insolubles were removed by filtration. The filtrate was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography (elution solvent; hexane:ethyl acetate=3:1) to obtain 7.5 g of (+)-(S)-2-methyl-3-(pent-4-en-2-ynyl)-cyclopent-2-en-4-one-1-ol.

Workup

  1. customA benzene layer was recovered from the mixture
  2. extractionthe water layer was further extracted with benzene
  3. additionThe benzene layers were mixed
  4. washwashed with saturated brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. distillationThe solvent was distilled off under reduced pressure
  7. additionMethanol was added to the residue, and insolubles
  8. customwere removed by filtration
  9. concentrationThe filtrate was concentrated under reduced pressure
  10. washthe residue was subjected to silica gel column chromatography (elution solvent; hexane:ethyl acetate=3:1)

Sources & evidence

ORD record
ord-d1ac541474ab4474a41013dc7bc46a71
Source dataset
uspto-grants-1993_07
Patent number
US05225605

Reaction notes

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