Tetrahydrofuran → tert-butyl (2S)-2-allylpyrrolidine-1-carboxylate

HRID 2181148Notes

Reaction equation

HRID 2181148 reaction equation
[CH:1]([Mg]Br)=[CH2:2].O1CCCC1.[C:10]([O:14][C:15]([N:17]1[CH2:21][CH2:20][CH2:19][C@H:18]1[CH2:22]I)=[O:16])([CH3:13])([CH3:12])[CH3:11].[NH4+].[Cl-]>C(OCC)C.[Cu]I>[C:10]([O:14][C:15]([N:17]1[CH2:21][CH2:20][CH2:19][C@H:18]1[CH2:22][CH:1]=[CH2:2])=[O:16])([CH3:13])([CH3:11])[CH3:12]

Participants

7

Reactant 4

HCID 8028TetrahydrofuranHCID 25517Ammonium ChlorideHCID 11312942(S)-2-Iodomethyl-pyrrolidine-1-carboxylic acid tert-butyl esterHCID 178418507HCID 178418507, compound

Product 1

HCID 15637736tert-butyl (2S)-2-allylpyrrolidine-1-carboxylate

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
-36 °C

Procedure

Under a nitrogen atmosphere, a solution of vinylmagnesium bromide, 1.0 M in tetrahydrofuran (2.0 mL, 2.0 mmol) was slowly added to a suspension of copper(I) iodide (244.9 mg, 1.28 mmol) in dry diethyl ether (10 mL) at −78° C. Upon completion of the addition, the mixture was warmed to −36° C. for 5 min and was then cooled to −78° C. A solution of (2S)-N-(tert-butoxycarbonyl)-2-(iodomethyl)pyrrolidine (200.0 mg, 0.64 mmol) in dry diethyl ether (5 mL) was added over a period of 10 min. The reaction mixture was warmed to −36° C. and was stirred at −36° C. for 6 h. The resulting dark mixture was treated with saturated aqueous NH4Cl solution (5 mL) and was stirred while warming to ambient temperature. The reaction mixture was extracted with diethyl ether (4×10 mL). The combined ether extracts were dried (Na2SO4), filtered and concentrated under vacuum to yield a pale-yellow oil (200 mg). The product was purified by column chromatography, eluting with hexane:ethyl acetate (1:1). Fractions containing the product were combined and concentrated under vacuum to afford 100 mg (73.6%) of an oil.

Workup

  1. additionUpon completion of the addition
  2. temperaturewas then cooled to −78° C
  3. temperatureThe reaction mixture was warmed to −36° C.
  4. stirringwas stirred
  5. temperaturewhile warming to ambient temperature
  6. extractionThe reaction mixture was extracted with diethyl ether (4×10 mL)
  7. dry with materialThe combined ether extracts were dried (Na2SO4)
  8. filtrationfiltered
  9. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-50c27c72ed5e4aadb62181daad5926e5
Source dataset
uspto-grants-2005_05
Patent number
US06890935B2

Reaction notes

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