Sodium Thiosulfate → Tert-butyl 3-oxopiperidine-1-carboxylate

HRID 899706Notes

Reaction equation

HRID 899706 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH2:11][CH:10]([OH:14])[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.C([O-])(O)=O.[Na+].S([O-])([O-])(=O)=S.[Na+].[Na+]>C(Cl)Cl>[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH2:11][C:10](=[O:14])[CH2:9]1)=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

6

Reactant 4

HCID 24477Sodium ThiosulfateHCID 159087TriacetoxyperiodinaneHCID 516892Sodium BicarbonateHCID 5456991-Boc-3-hydroxypiperidine

Product 1

HCID 2756825Tert-butyl 3-oxopiperidine-1-carboxylateYield 95.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a solution of 3-hydroxy-piperidine-1-carboxylic acid tert-butyl ester (1.9169 g, 9.5 mmol) in CH2Cl2 (50 mL) was added Dess-Martin Periodinane (4.8470 g, 11.4 mmol), and the mixture was stirred at room temperature for 5 hours. CH2Cl2 (75 mL), saturated NaHCO3 (100 mL), and 20% aqueous sodium thiosulfate (100 mL) were added, and the mixture was stirred for 30 minutes. The layers were separated, and the aqueous layer was extracted with CH2Cl2 (1×75 mL). The organic extracts were washed with brine (1×100 mL), dried (Na2SO4), and concentrated. Purification of the crude material by column chromatography on silica gel (4:1 hexanes-EtOAc) provided 1.80 g (95%) of 3-oxo-piperidine-1-carboxylic acid tert-butyl ester as a colorless oil. 1H NMR (CDCl3) δ 1.49 (s, 9H), 1.93-2.02 (m, 2H), 2.46 (t, 2H, J=6 Hz), 3.58 (t, 2H, J=6 Hz), 4.00 (s, 2H).

Workup

  1. stirringthe mixture was stirred for 30 minutes
  2. customThe layers were separated
  3. extractionthe aqueous layer was extracted with CH2Cl2 (1×75 mL)
  4. washThe organic extracts were washed with brine (1×100 mL)
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated
  7. customPurification of the crude material by column chromatography on silica gel (4:1 hexanes-EtOAc)

Sources & evidence

ORD record
ord-304fe40845d542b285f6e7fea63dea2b
Source dataset
uspto-grants-2008_04
Patent number
US07354932B2

Reaction notes

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