Allyl bromide → 1-tert-butyl 2-methyl (2R,4R)-4-allyloxypyrrolidine-1,2-dicarboxylate

HRID 602348Notes

Reaction equation

HRID 602348 reaction equation
[H-].[Na+].[OH:3][C@H:4]1[CH2:8][N:7]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[C@@H:6]([C:16]([O:18][CH3:19])=[O:17])[CH2:5]1.Br[CH2:21][CH:22]=[CH2:23]>CN(C)C=O.[Ag]=O>[CH2:23]([O:3][C@H:4]1[CH2:8][N:7]([C:9]([O:11][C:12]([CH3:13])([CH3:14])[CH3:15])=[O:10])[C@@H:6]([C:16]([O:18][CH3:19])=[O:17])[CH2:5]1)[CH:22]=[CH2:21]

Participants

6

Reactant 3

HCID 7841Allyl bromideHCID 24758Sodium hydrideHCID 6951202(2R,4R)-4-Hydroxy-pyrrolidine-1,2-dicarboxylic acid 1-tert-butyl ester 2-methyl ester

Product 1

HCID 586912241-tert-butyl 2-methyl (2R,4R)-4-allyloxypyrrolidine-1,2-dicarboxylateYield 96.8%

Reagents, catalysts & solvents 2

HCID 92152Silver(II) oxideCatalystHCID 6228DimethylformamideSolvent

Procedure

1.55 g (38.6 mmol) of sodium hydride are added in portions under nitrogen to the solution of 10.3 g (42 mmol) of 1-tert-butyl 2-methyl (2R,4R)-4-hydroxypyrrolidine-1,2-dicarboxylate and 36.34 ml (420 mmol) of 3-bromo-1-propene in 100 ml of dimethylformamide (DMF), and the mixture is subsequently stirred at room temperature for 15 minutes. 9.73 g (42 mmol) of silver oxide are then added in portions to the reaction mixture, and the reaction mixture is left to stir at room temperature for a further 12 hours. The reaction mixture is then filtered, the filtrate is evaporated to dryness under reduced pressure, and the residue is taken up in 20 ml of saturated citric acid solution. After the precipitate has been filtered off, the filtrate is extracted twice with 20 ml of ethyl acetate each time. Drying of the combined organic phases over sodium sulfate and stripping-off of the solvent gives 11.6 g of 1-tert-butyl 2-methyl (2R,4R)-4-allyloxypyrrolidine-1,2-dicarboxylate as a red-brown oil; ESI 286.

Workup

  1. waitthe reaction mixture is left
  2. stirringto stir at room temperature for a further 12 hours
  3. filtrationThe reaction mixture is then filtered
  4. customthe filtrate is evaporated to dryness under reduced pressure
  5. filtrationAfter the precipitate has been filtered off
  6. extractionthe filtrate is extracted twice with 20 ml of ethyl acetate each time
  7. dry with materialDrying of the combined organic phases over sodium sulfate and stripping-off of the solvent

Sources & evidence

ORD record
ord-740750c8959d4a6b927be85ae6fd8b28
Source dataset
uspto-grants-2011_03
Patent number
US07906516B2

Reaction notes

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