Dimethyl Sulfoxide → Tert-butyl 3-oxopiperidine-1-carboxylate

HRID 744115Notes

Reaction equation

HRID 744115 reaction equation
CS(C)=O.C(Cl)(=O)C(Cl)=O.[C:11]([O:15][C:16]([N:18]1[CH2:23][CH2:22][CH2:21][CH:20]([OH:24])[CH2:19]1)=[O:17])([CH3:14])([CH3:13])[CH3:12].C(N(CC)CC)C>C(Cl)Cl>[C:11]([O:15][C:16]([N:18]1[CH2:23][CH2:22][CH2:21][C:20](=[O:24])[CH2:19]1)=[O:17])([CH3:14])([CH3:12])[CH3:13]

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 5456991-Boc-3-hydroxypiperidine

Product 1

HCID 2756825Tert-butyl 3-oxopiperidine-1-carboxylateYield 93.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a cooled (-65° C.) solution of DMSO (1.42 ml; 20 mmol) in CH2Cl2 (30 ml) was added oxalyl chloride (0.87 ml; 10 mmol). The resulting suspension was stirred for an additional 15 minutes at -65° C., whereupon the product of Step A (2.17 g; 10 mmol) dissolved in 5 ml of CH2Cl2 was added portionwise and the reaction was stirred for an additional 15 minutes at that temperature. Triethylamine (5.56 ml; 40 mmol) was then added dropwise, and the solution was allowed to warm to room temperature, whereupon the reaction was stirred for an additional 1.5 hours. The reaction was quenched with H2O and extracted several times with EtOAc. The combined organic phase was washed with 10% aqueous citric acid, H2O, saturated aqueous NaCl, dried (MgSO4), filtered and evaporated. The residue was purified on a silica gel flash chromatography column eluted with 25% EtOAc-hexanes. The fractions containing pure material were combined and concentrated in vacuo to afford 1.87 g of the title compound as a yellow oil.

Workup

  1. additionwas added portionwise
  2. stirringwas stirred for an additional 1.5 hours
  3. customThe reaction was quenched with H2O
  4. extractionextracted several times with EtOAc
  5. washThe combined organic phase was washed with 10% aqueous citric acid, H2O, saturated aqueous NaCl
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. customevaporated
  9. customThe residue was purified on a silica gel flash chromatography column
  10. washeluted with 25% EtOAc-hexanes
  11. additionThe fractions containing pure material
  12. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-d77a3a77d29842989b0eff3d8c9feb8e
Source dataset
uspto-grants-1996_09
Patent number
US05559128

Reaction notes

Loading…