Allyl iodide → 1-Benzyl 4-methyl 4-allylpiperidine-1,4-dicarboxylate

HRID 215947Notes

Reaction equation

HRID 215947 reaction equation
C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[N:11]1([C:21]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)=[O:22])[CH2:16][CH2:15][CH:14]([C:17]([O:19][CH3:20])=[O:18])[CH2:13][CH2:12]1.I[CH2:32][CH:33]=[CH2:34]>C1COCC1>[CH2:34]([C:14]1([C:17]([O:19][CH3:20])=[O:18])[CH2:13][CH2:12][N:11]([C:21]([O:23][CH2:24][C:25]2[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=2)=[O:22])[CH2:16][CH2:15]1)[CH:33]=[CH2:32]

Participants

5

Reactant 3

HCID 11166Allyl iodideHCID 15125441-Benzyl 4-methyl piperidine-1,4-dicarboxylateHCID 2733832Lithium Hexamethyldisilazide

Product 1

HCID 588931861-Benzyl 4-methyl 4-allylpiperidine-1,4-dicarboxylateYield 91%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-50 °C

Procedure

Lithium bis(trimethylsilyl)amide (LiHMDS) in THF (1.0 M, 45 mL) was added to a solution of 1-benzyl 4-methyl piperidine-1,4-dicarboxylate (10.0 g, 0.0360 mol) at −78° C. The reaction mixture was slowly warmed to −50° C. and kept at this temperature for 10 min, and then re-cooled to −78° C. 3-Iodo-1-propene (4.95 mL, 0.0541 mol) was added slowly. After the addition, the mixture was allowed to warm slowly to room temperature and kept at room temperature for 3 hours. The mixture was carefully quenched (the pH was adjusted to 4) with 1N HCl solution, and ethyl acetate (200 mL) was added. The organic layer was separated and washed with water, NaHCO3 (7.5%), brine, dried over MgSO4, and filtered. The filtrate was concentrated. The residue was purified by flash chromatography with 20% ethyl acetate in hexane to give 1-benzyl 4-methyl 4-allylpiperidine-1,4-dicarboxylate (10.4 g, 90.9%).

Workup

  1. temperaturere-cooled to −78° C
  2. additionAfter the addition
  3. temperatureto warm slowly to room temperature
  4. waitkept at room temperature for 3 hours
  5. customThe mixture was carefully quenched (the pH
  6. additionwas added
  7. customThe organic layer was separated
  8. washwashed with water, NaHCO3 (7.5%), brine
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. concentrationThe filtrate was concentrated
  12. customThe residue was purified by flash chromatography with 20% ethyl acetate in hexane

Sources & evidence

ORD record
ord-98fd19bc7d554feaaaa0296872952538
Source dataset
uspto-grants-2012_06
Patent number
US08193207B2

Reaction notes

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