(+-)-1-(tert-Butoxycarbonyl)pyrrolidine-3-carboxaldehyde → tert-Butyl 3-ethenylpyrrolidine-1-carboxylate

HRID 1396030Notes

Reaction equation

HRID 1396030 reaction equation
[CH2:1]([Li])CCC.[C:6]([O:10][C:11]([N:13]1[CH2:17][CH2:16][CH:15]([CH:18]=O)[CH2:14]1)=[O:12])([CH3:9])([CH3:8])[CH3:7]>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[C:6]([O:10][C:11]([N:13]1[CH2:17][CH2:16][CH:15]([CH:18]=[CH2:1])[CH2:14]1)=[O:12])([CH3:9])([CH3:8])[CH3:7]

Participants

5

Reactant 2

HCID 4692112(+-)-1-(tert-Butoxycarbonyl)pyrrolidine-3-carboxaldehydeHCID 178418339Butyllithium

Product 1

HCID 53302213tert-Butyl 3-ethenylpyrrolidine-1-carboxylateYield 70%

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To a suspension consisting of methyl triphenylphosphonium bromide (4.76 g, 13.3 mmol) and THF (20 mL) at 0° C. was added n-butyl lithium (1.6 M solution in hexanes, 8.3 mL). The resulting orange solution was stirred at 0° C. for 5 min. A solution consisting of 3-formyl-pyrrolidine-1-carboxylic acid tert-butyl ester (2.50 g, 12.5 mmol) and THF (15 mL) was then added via cannula. The reaction mixture was stirred at 0° C. and was warmed to rt over 2.5 h. The reaction mixture was then cooled to 0° C., quenched with sat. NH4Cl, and extracted with Et2O. The organic layer was combined, dried (MgSO4) and concentrated. The crude residue was suspended in hot hexanes and filtered. The filtrate was concentrated and purified (FCC) to give the title compound (1.7 g, 70%).

Workup

  1. additionwas then added via cannula
  2. stirringThe reaction mixture was stirred at 0° C.
  3. temperaturewas warmed to rt over 2.5 h
  4. temperatureThe reaction mixture was then cooled to 0° C.
  5. customquenched with sat. NH4Cl
  6. extractionextracted with Et2O
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated
  9. filtrationfiltered
  10. concentrationThe filtrate was concentrated
  11. custompurified (FCC)

Sources & evidence

ORD record
ord-2e8c36f4973d40d08216969e60a6b094
Source dataset
uspto-grants-2014_12
Patent number
US08901111B2

Reaction notes

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