Dimethyl Sulfoxide → HCID 12140788, compound

HRID 2414685Notes

Reaction equation

HRID 2414685 reaction equation
CS(C)=O.[C:5](Cl)(=O)C(Cl)=O.[C:11]([O:15][C:16]([N:18]([CH2:26][CH2:27][CH2:28]O)[CH2:19][CH2:20][C:21]([O:23][CH2:24][CH3:25])=[O:22])=[O:17])([CH3:14])([CH3:13])[CH3:12].C(N(CC)CC)C>ClCCl.[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1>[C:11]([O:15][C:16]([N:18]([CH2:26][CH2:27][CH:28]=[CH2:5])[CH2:19][CH2:20][C:21]([O:23][CH2:24][CH3:25])=[O:22])=[O:17])([CH3:12])([CH3:13])[CH3:14]

Participants

8

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 22645249HCID 22645249, compound

Product 1

HCID 12140788HCID 12140788, compoundYield 76.1%

Reagents, catalysts & solvents 3

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 6344DichloromethaneSolvent3×HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of dimethylsulfoxide (DMSO) (1.11 mL, 5.81 mmol) in dichloromethane (DCM)(15 mL) was added dropwise a solution of oxalyl chloride (1.01 mL, 11.62 mmol) in DCM (5 mL) at −78° C. To the mixture was added a solution of ethyl N-(tert-butoxycarbonyl)-3-(3-hydroxypropylamino)propionate (1.6 g, 5.81 mmol) in DCM (10 mL) after 30 minutes. The mixture was stirred for 30 minutes at −78° C., then triethylamine (5.91 mL) was added. After stirring for 30 minutes at room temperature, the mixture was quenched by a saturated aqueous NH4Cl solution, and extracted with DCM. The organic layer was washed with water and brine, dried over Na2SO4, and evaporated in vacuo. The residue was dissolved in THF (20 mL), then a Wittig reagent, which was prepared from methyltriphenylphosphonium bromide (2.49 g, 22.2 mmol) and 1N tert-BuOK THF solution (6.97 mL) in THF (10 mL), was added to the solution at 0° C. The mixture was stirred for an hour at room temperature, then quenched by a saturated aqueous NH4Cl solution, and extracted with ethyl acetate. The organic layer was washed with water and brine, dried over Na2SO4, and evaporated in vacuo. The residue was purified by a silica gel column chromatography eluting with a mixture of ethyl acetate and n-hexane (1:10) to give ethyl N-(tert-butoxycarbonyl)-3-(3-butenylamino)propionate (1.2 g, 0.44 mmol, 76.1%) as a colourless oil.

Workup

  1. stirringAfter stirring for 30 minutes at room temperature
  2. customthe mixture was quenched by a saturated aqueous NH4Cl solution
  3. extractionextracted with DCM
  4. washThe organic layer was washed with water and brine
  5. dry with materialdried over Na2SO4
  6. customevaporated in vacuo
  7. dissolutionThe residue was dissolved in THF (20 mL)
  8. additionwas added to the solution at 0° C
  9. stirringThe mixture was stirred for an hour at room temperature
  10. customquenched by a saturated aqueous NH4Cl solution
  11. extractionextracted with ethyl acetate
  12. washThe organic layer was washed with water and brine
  13. dry with materialdried over Na2SO4
  14. customevaporated in vacuo
  15. customThe residue was purified by a silica gel column chromatography
  16. washeluting with a mixture of ethyl acetate and n-hexane (1:10)

Sources & evidence

ORD record
ord-491e281e091042f0ab800c848a4acf28
Source dataset
uspto-grants-2004_11
Patent number
US06812235B2

Reaction notes

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