Sodium Carbonate → Tert-butyl (2r)-2-(2,2-dibromovinyl)pyrrolidine-1-carboxylate

HRID 846661Notes

Reaction equation

HRID 846661 reaction equation
[C:1]([Br:5])(Br)(Br)[Br:2].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH:25]([C@H:27]1[CH2:31][CH2:30][CH2:29][N:28]1[C:32]([O:34][C:35]([CH3:38])([CH3:37])[CH3:36])=[O:33])=O.C(=O)([O-])[O-].[Na+].[Na+]>C(Cl)Cl.O.C(OCC)(=O)C>[Br:2][C:1]([Br:5])=[CH:25][C@H:27]1[CH2:31][CH2:30][CH2:29][N:28]1[C:32]([O:34][C:35]([CH3:36])([CH3:38])[CH3:37])=[O:33]

Participants

8

Reactant 4

HCID 10340Sodium CarbonateHCID 11205Carbon tetrabromideHCID 11776TriphenylphosphineHCID 7009153N-(tert-Butoxycarbonyl)-D-prolinal

Product 1

HCID 14730282Tert-butyl (2r)-2-(2,2-dibromovinyl)pyrrolidine-1-carboxylateYield 91%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

Carbon tetrabromide (49.2 g, 0.15 mol) in methylene chloride (150 mL) was added at 0° C. to a stirred solution of triphenyl phosphine (78.2 g, 0.30 mol) in methylene chloride (600 mL) under nitrogen. The solution was stirred at 0° C. for 1 hr. and (R)-t-butyl 2-formyl-1-pyrrolidinecarboxylate (21.9 g, 0.10 mol) was added. After 30 min. a solution of sodium carbonate (75 g, 0.75 mol) in water (300 mL) was added. The phases were separated and the aqueous phase was reextracted with methylene chloride (200 mL). The organic phase was washed with water (40 mL), and the majority of solvent was removed under reduced pressure leaving the material in a minimum of methylene chloride. Ethyl acetate (500 mL) was added and the resulting precipitate of triphenylphosphine oxide was filtered off. The mother liquors were evaporated and filtered repeatedly to remove additional triphenylphosphine oxide. The residual solid in ethyl acetate was then concentrated and applied to a silica gel column. Elution with ethyl acetate:Skellysolve B (1:10) gave 31.6 g (91%) of product. This was crystallized from petroleum ether to give 25.8 g of product, m.p. 64°-67° C. The analytical sample was recrystallized from ethyl acetate:Skellysolve B. [α]D -21° (c 0.81, MeOH).

Workup

  1. customThe phases were separated
  2. washThe organic phase was washed with water (40 mL)
  3. customthe majority of solvent was removed under reduced pressure
  4. customleaving the material in a minimum of methylene chloride
  5. filtrationthe resulting precipitate of triphenylphosphine oxide was filtered off
  6. customThe mother liquors were evaporated
  7. filtrationfiltered repeatedly
  8. customto remove additional triphenylphosphine oxide
  9. concentrationThe residual solid in ethyl acetate was then concentrated
  10. washElution with ethyl acetate:Skellysolve B (1:10)

Sources & evidence

ORD record
ord-f17b7dcbaec94504950cf6b65030f650
Source dataset
uspto-grants-1992_08
Patent number
US05137905

Reaction notes

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