Sodium Carbonate → 1-(2-Pyridin-3-yl-allyl)-pyrrolidin-2-one

HRID 2084066Notes

Reaction equation

HRID 2084066 reaction equation
Br[C:2](=[CH2:10])[CH2:3][N:4]1[CH2:8][CH2:7][CH2:6][C:5]1=[O:9].C(=O)([O-])[O-].[Na+].[Na+].[N:17]1[CH:22]=[CH:21][CH:20]=[C:19]([Sn](CCCC)(CCCC)CCCC)[CH:18]=1.B([O-])(OC)OC.[Li].B(OC)(OC)OC>C(O)C.C1C=CC=CC=1>[N:17]1[CH:22]=[CH:21][CH:20]=[C:19]([C:2](=[CH2:10])[CH2:3][N:4]2[CH2:8][CH2:7][CH2:6][C:5]2=[O:9])[CH:18]=1

Participants

7

Reactant 5

HCID 10340Sodium CarbonateHCID 2977311-(2-Bromoallyl)-pyrrolidin-2-oneHCID 34838483-(Tributylstannyl)pyridineHCID 85966883Dimethyl borateHCID 86588581Trimethyl borate lithium salt

Product 1

HCID 227330911-(2-Pyridin-3-yl-allyl)-pyrrolidin-2-oneYield 82%

Reagents, catalysts & solvents 1

HCID 21965192Npc112006Solvent

Procedure

To a suspension of 5.0 g (40.6 mmol) of pyrrolidinone potassium salt prepared from Example 1 in 40 mL of toluene, solution of 5.24 mL (2 equiv.) of 2,3-dibromopropene in 10 mL of toluene was added dropwise for 1 hour in water bath and the reaction mixture was reacted at 60˜70° C. for 2 hours. Upon completion of the reaction, the mixture was cooled to 0° C. and filtered to remove solid. It was then concentrated under reduced pressure and purified by separation with silica gel column chromatography (ethyl acetate/n-hexane (1:1)) to obtain 5.30 g (64% yield) of 1-(2-bromoallyl)-pyrrolidin-2-one. To degassed solution of 1.0 g (4.90 mmol) of 1-(2-bromoallyl)-pyrrolidin-2-one prepared in the above in 50 mL of ethanol/benzene (1:1), 5 mol% (172 mg) of ditriphenylphosphine palladium dichloride, degassed solution of 7.35 mL of 2N sodium carbonate and 3-pyridyl-tributyltin, dimethyl borate, trimethyl borate lithium salt, boronic acid propanediol ring ester (2 equiv.), etc. were added. The mixture was reacted for 15 minutes at room temperature, followed by heating at reflux for 18 hours. After concentrating under reduced pressure, it was extracted with ethyl acetate for three times and washed with brine for two times. The concentrated solution was purified by separation with silica gel column chromatography (ethyl acetate followed by methylene chloride/methanol (20:1)) to obtain 810 mg (82% yield) of 1-(2-pyridin-3-yl-allyl)-pyrrolidin-2-one. Ozones were added to solution of 100 mg (0.494 mmol) of 1-(2-pyridin-3-yl-allyl)-pyrrolidin-2-one at −78° C. to obtain 1-(2-oxo-2-pyridin-3-yl-ethyl)-pyrrolidin-2-one, which was the same as synthesized in Example 20.

Workup

  1. additionwere added
  2. customThe mixture was reacted for 15 minutes at room temperature
  3. temperatureby heating
  4. temperatureat reflux for 18 hours
  5. concentrationAfter concentrating under reduced pressure, it
  6. extractionwas extracted with ethyl acetate for three times
  7. washwashed with brine for two times
  8. customThe concentrated solution was purified by separation with silica gel column chromatography (ethyl acetate followed by methylene chloride/methanol (20:1))

Sources & evidence

ORD record
ord-c57e6a68a1604afe91ff6fab13cddb42
Source dataset
uspto-grants-2004_04
Patent number
US06716857B2

Reaction notes

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