3-Boc-2,2-dimethyloxazolidine-4-carboxaldehyde, (S)-(-)- → HCID 9880121, compound

HRID 1797293Notes

Reaction equation

HRID 1797293 reaction equation
CC(C)([O-])C.[K+].[Cl-].[N+](C1C=CC=CC=1C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([O-])=O.C([C@@H]1COC(C)(C)N1C(OC(C)(C)C)=O)=O.[CH3:53][C:54]1([CH3:77])[N:58]([C:59]([O:61][C:62]([CH3:65])([CH3:64])[CH3:63])=[O:60])[C@H:57]([CH:66]=[CH:67][C:68]2[CH:73]=[CH:72][CH:71]=[CH:70][C:69]=2[N+:74]([O-])=O)[CH2:56][O:55]1>O1CCOCC1.CCOC(C)=O.[Pd].O>[NH2:74][C:69]1[CH:70]=[CH:71][CH:72]=[CH:73][C:68]=1[CH2:67][CH2:66][C@@H:57]1[CH2:56][O:55][C:54]([CH3:77])([CH3:53])[N:58]1[C:59]([O:61][C:62]([CH3:65])([CH3:64])[CH3:63])=[O:60]

Participants

9

Reactant 4

HCID 1798243-Boc-2,2-dimethyloxazolidine-4-carboxaldehyde, (S)-(-)-HCID 22174467HCID 22174467, compoundHCID 23665647Potassium tert-butoxideHCID 86759993HCID 86759993, compound

Product 1

HCID 9880121HCID 9880121, compound

Reagents, catalysts & solvents 4

HCID 23938PalladiumCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent2×

Procedure

Potassium tert-butoxide (498 mg, 4.44 mmol) was added to a solution of (2-nitrobenzyl)triphenylphosphonium chloride (2.04 g, 4.89 mmol) in 1,4-dioxane (10 mL) under an atmosphere of argon. The mixture was stirred for 30 min at room temperature and then at 80° C. for 40 min. A solution of tert-butyl (4S)-4-formyl-2,2-dimethyl-oxazolidine-3-carboxylate (510 mg, 2.22 mmol) in 1,4 dioxane (3.0 mL) was added with a syringe. The resulting mixture was refluxed for 4 h and then allowed to come to room temperature overnight. The reaction mixture was poured into water and extracted with EtOAc (×3). The organic phases were combined and washed with brine and dried with MgSO4. The crude product was purified by flash chromatography eluting with petroleum ether/EtOAc 9:1 to afford a (Z)/(E) mixture of tert-Butyl (4R)-2,2-dimethyl-4-[2-(2-nitrophenyl)vinyl]-1,3-oxazolidine-3-carboxylate as a yellow oil. 288 mg of the obtained product was dissolved in EtOAc (10 ml), added Pd/C (40 mg, 10%) and then stirred under an atmosphere of hydrogen (1 atm) for 4 h. The reaction mixture was filtered through a pad of decalite and concentrated in vacuo. The crude product was purified by flash chromatography eluting with petroleum ether/EtOAc 2:1 to afford the title compound as a white solid.

Workup

  1. waitat 80° C. for 40 min
  2. temperatureThe resulting mixture was refluxed for 4 h
  3. waitto come to room temperature overnight
  4. extractionextracted with EtOAc (×3)
  5. washwashed with brine
  6. dry with materialdried with MgSO4
  7. customThe crude product was purified by flash chromatography
  8. washeluting with petroleum ether/EtOAc 9:1
  9. customto afford a (
  10. stirringstirred under an atmosphere of hydrogen (1 atm) for 4 h
  11. filtrationThe reaction mixture was filtered through a pad of decalite
  12. concentrationconcentrated in vacuo
  13. customThe crude product was purified by flash chromatography
  14. washeluting with petroleum ether/EtOAc 2:1

Sources & evidence

ORD record
ord-81b3d2919111408bbe1fa78f30f19798
Source dataset
uspto-grants-2006_04
Patent number
US07034015B2

Reaction notes

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