Methyl morpholine oxide → tert-Butyl 4-formylpiperidine-1-carboxylate

HRID 899730Notes

Reaction equation

HRID 899730 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH:11]([CH2:14][OH:15])[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C[N+]1([O-])CCOCC1>C(Cl)Cl.[Ru]([O-])(=O)(=O)=O.C([N+](CCC)(CCC)CCC)CC>[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH:11]([CH:14]=[O:15])[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 2

HCID 82029Methyl morpholine oxideHCID 2764081Tert-butyl 4-(hydroxymethyl)piperidine-1-carboxylate

Product 1

HCID 1514430tert-Butyl 4-formylpiperidine-1-carboxylateYield 20.8%

Reagents, catalysts & solvents 2

HCID 178419074HCID 178419074, compoundCatalystHCID 6344DichloromethaneSolvent

Procedure

To a solution of the above alcohol (0.437 g, 2.03 mmol) in CH2Cl2 (10 mL), at room temperature, was added sequentially 3 Å molecular sieves (1.07 g), N-methylmorpholine N-oxide (0.365 g, 3.11 mmol), and tetrapropylammonium perruthenate (70 mg, 0.20 mmol). After 1 hour, the mixture was filtered through a short column of silica gel and the cake was washed with ethyl acetate. The solvent was removed from the filtrate under reduced pressure. Purification of the crude material by column chromatography on silica gel (4:1 hexanes-ethyl acetate) provided 90 mg (20%) of 1-(tert-butoxycarbonyl)-piperidine-4-carboxaldehyde as a colorless oil. 1H NMR (CDCl3) δ 1.46 (s, 9H), 1.51-1.62 (m, 2H), 1.85-1.93 (m, 2H), 2.37-2.46 (m, 1H), 2.88-2.97 (m, 2H), 3.94-4.00 (m, 2H), 9.66 (s, 1H).

Workup

  1. filtrationthe mixture was filtered through a short column of silica gel
  2. washthe cake was washed with ethyl acetate
  3. customThe solvent was removed from the filtrate under reduced pressure
  4. customPurification of the crude material by column chromatography on silica gel (4:1 hexanes-ethyl acetate)

Sources & evidence

ORD record
ord-68c422e84ff940a4914fc39c053e965d
Source dataset
uspto-grants-2008_04
Patent number
US07354934B2

Reaction notes

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