1-Benzyl 4-methyl 4-allylpiperidine-1,4-dicarboxylate → 1-Benzyl 4-methyl 4-(2-oxoethyl)piperidine-1,4-dicarboxylate

HRID 1864915Notes

Reaction equation

HRID 1864915 reaction equation
[CH2:1]([C:4]1([C:20]([O:22][CH3:23])=[O:21])[CH2:9][CH2:8][N:7]([C:10]([O:12][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[O:11])[CH2:6][CH2:5]1)[CH:2]=C.C1C=C[NH+]=CC=1.[O-:30][Cr](Cl)(=O)=O>C1COCC1.C(Cl)Cl.CCOCC>[O:30]=[CH:2][CH2:1][C:4]1([C:20]([O:22][CH3:23])=[O:21])[CH2:9][CH2:8][N:7]([C:10]([O:12][CH2:13][C:14]2[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=2)=[O:11])[CH2:6][CH2:5]1

Participants

6

Reactant 2

HCID 588931861-Benzyl 4-methyl 4-allylpiperidine-1,4-dicarboxylateHCID 178418287HCID 178418287, compound

Product 1

HCID 588931821-Benzyl 4-methyl 4-(2-oxoethyl)piperidine-1,4-dicarboxylate

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 1-benzyl 4-methyl 4-allylpiperidine-1,4-dicarboxylate from Step B (4.45 g, 14.0 mmol) in THF (70 mL) at 0° C. was added borane-methyl sulfide complex (28.0 mL of a 2M solution in THF, 56.1 mmol). The reaction mixture was slowly warmed to ambient temperature and stirred for 16 h, then quenched with water and concentrated in vacuo. The residue was dissolved in CH2Cl2 (140 mL) and added drop wise to a solution of PCC (6.65 g. 30.8 mmol) and 4 Å molecular sieves (6.65 g) in CH2Cl2 (50 mL) at 0° C. The reaction mixture was warmed to ambient temperature and stirred for 16 h, then diluted with ether (200 mL) and filtered through a pad of celite. Additional ether was used to wash the celite. The combined organics were concentrated in vacuo to give a residue that was purified by silica gel chromatography, eluting with a gradient of CH2Cl2:MeOH-100:0 to 95:5, to give the title compound. MS: m/z=356 (M+Na).

Workup

  1. customquenched with water
  2. concentrationconcentrated in vacuo
  3. dissolutionThe residue was dissolved in CH2Cl2 (140 mL)
  4. temperatureThe reaction mixture was warmed to ambient temperature
  5. stirringstirred for 16 h
  6. filtrationfiltered through a pad of celite
  7. washto wash the celite
  8. concentrationThe combined organics were concentrated in vacuo
  9. customto give a residue that
  10. customwas purified by silica gel chromatography
  11. washeluting with a gradient of CH2Cl2

Sources & evidence

ORD record
ord-9495b06a2b7f47d689f4fb3ebd02d74b
Source dataset
uspto-grants-2009_12
Patent number
US07625901B2

Reaction notes

Loading…