Triacetoxyperiodinane → 1,1-Dimethylethyl 4-Ethenyl-4-(phenylmethoxymethyl)-1-piperidinecarboxylate

HRID 2213030Notes

Reaction equation

HRID 2213030 reaction equation
[CH3:1]C(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C1=CC=CC=2)=O.O[CH2:24][C:25]1([CH2:38][O:39][CH2:40][C:41]2[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=2)[CH2:30][CH2:29][N:28]([C:31]([O:33][C:34]([CH3:37])([CH3:36])[CH3:35])=[O:32])[CH2:27][CH2:26]1.S(=O)(O)[O-].[Na+].C(=O)([O-])O.[Na+]>ClCCl>[CH:24]([C:25]1([CH2:38][O:39][CH2:40][C:41]2[CH:42]=[CH:43][CH:44]=[CH:45][CH:46]=2)[CH2:30][CH2:29][N:28]([C:31]([O:33][C:34]([CH3:36])([CH3:35])[CH3:37])=[O:32])[CH2:27][CH2:26]1)=[CH2:1]

Participants

6

Reactant 4

HCID 159087TriacetoxyperiodinaneHCID 516892Sodium BicarbonateHCID 219551981-Boc-4-(hydroxymethyl)-4-[(benzyloxy)methyl]piperidineHCID 23665763Sodium Bisulfite

Product 1

HCID 219553091,1-Dimethylethyl 4-Ethenyl-4-(phenylmethoxymethyl)-1-piperidinecarboxylateYield 101.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

1,1,1-Tris(acetyloxy)-1,1-dihydro-1,2-benziodoxol-3(1H)-one (1.38 g, 3.3 mmol) was added to a solution of 1,1-dimethylethyl 4-(hydroxymethyl)-4-(phenylmethoxymethyl)-1-piperidinecarboxylate (Description 95, 1.06 g, 3 mmol) in dichloromethane (40 mL) and the mixture was stirred at room temperature for 4 hours. Aqueous sodium bisulfite (10%, 10 mL) was added and the mixture was stirred at room temperature for 5 minutes. Saturated aqueous sodium hydrogen carbonate (20 mL) was added and the layers were separated. The organic layer was dried (MgSO4) and the solvent was evaporated under reduced pressure. The residue was dissolved in tetrahydrofuran (20 mL), and added to a stirred, cooled (0° C.) solution of triphenylphosphoranylidine (0.1M, 50 mL). The mixture was stirred at room temperature for 16 hours, then the solvent was evaporated under reduced pressure. Ethyl acetate (40 mL) and aqueous sodium hydrogen carbonate (10%, 40 mL) were added and the layers were separated. The organic layer was dried (MgSO4) and the solvent was evaporated under reduced pressure. The residue was purified by flash column chromatography on silica gel, eluting with isohexane/EtOAc (75:25) give the title compound (1.01 g, 99%). m/z (ES+) 332 (M+1).

Workup

  1. stirringthe mixture was stirred at room temperature for 5 minutes
  2. customthe layers were separated
  3. dry with materialThe organic layer was dried (MgSO4)
  4. customthe solvent was evaporated under reduced pressure
  5. dissolutionThe residue was dissolved in tetrahydrofuran (20 mL)
  6. additionadded to a stirred
  7. temperaturecooled (0° C.) solution of triphenylphosphoranylidine (0.1M, 50 mL)
  8. stirringThe mixture was stirred at room temperature for 16 hours
  9. customthe solvent was evaporated under reduced pressure
  10. additionEthyl acetate (40 mL) and aqueous sodium hydrogen carbonate (10%, 40 mL) were added
  11. customthe layers were separated
  12. dry with materialThe organic layer was dried (MgSO4)
  13. customthe solvent was evaporated under reduced pressure
  14. customThe residue was purified by flash column chromatography on silica gel
  15. washeluting with isohexane/EtOAc (75:25)

Sources & evidence

ORD record
ord-faf33270296f4658b32b656d9e75887d
Source dataset
uspto-grants-2006_09
Patent number
US07105507B2

Reaction notes

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