Tetrahydrofuran → 1-Boc-4-Methylenepiperidine

HRID 1785272Notes

Reaction equation

HRID 1785272 reaction equation
O=[C:2]1[CH2:7][CH2:6][N:5]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:4][CH2:3]1.O1CCC[CH2:16]1>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C([Li])CCC.CCCCCC.C(OCC)(=O)C>[CH2:16]=[C:2]1[CH2:7][CH2:6][N:5]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:4][CH2:3]1

Participants

6

Reactant 2

HCID 8028Tetrahydrofuran2×HCID 735900tert-Butyl 4-oxopiperidine-1-carboxylate

Product 1

HCID 27568081-Boc-4-Methylenepiperidine

Reagents, catalysts & solvents 3

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8857Ethyl AcetateSolventHCID 178418244HCID 178418244, compoundSolvent

Procedure

To a solution of 986 mg of methyltriphenylphosphonium bromide in 20 ml of tetrahydrofuran, 1.87 ml of 1.63 M n-butyl lithium/hexane solution was added dropwise at 0° C., under cooling with ice. The temperature then was immediately raised to room temperature, and the system was stirred for 50 minutes. The reaction liquid was again cooled to 0° C., to which a solution of 500 mg of t-butyl 4-oxotetrahydropyridine-1(2H)-carboxylate in 5 ml of tetrahydrofuran was added dropwise, followed by an hour's stirring at the same temperature. The reaction liquid was diluted with ethyl acetate, washed successively with saturated aqueous ammonium chloride solution and saturated brine, and dried over anhydrous sodium sulfate. Distilling the solvent off under reduced pressure, the resulting residue was purified on silica gel column chromatography (eluent: hexane/ethyl acetate=5/1) to provide 192 mg of the title compound.

Workup

  1. temperatureunder cooling with ice
  2. customThe reaction liquid
  3. additionwas added dropwise
  4. waitfollowed by an hour
  5. stirring's stirring at the same temperature
  6. customThe reaction liquid
  7. washwashed successively with saturated aqueous ammonium chloride solution and saturated brine
  8. dry with materialdried over anhydrous sodium sulfate
  9. distillationDistilling the solvent off under reduced pressure
  10. customthe resulting residue was purified on silica gel column chromatography (eluent: hexane/ethyl acetate=5/1)

Sources & evidence

ORD record
ord-27b625f7f1d74977bde5b563f9b0aa0a
Source dataset
uspto-grants-2009_03
Patent number
US07504432B2

Reaction notes

Loading…