Dichloromethane → (4R,5S)-4-Methyl-3-((R)-4-methyl-octanoyl)-5-phenyl-oxazolidin-2-one

HRID 479051Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 479051
[CH3:1][C@H:2]([CH2:8][CH2:9][CH2:10][CH3:11])[CH2:3][CH2:4][C:5]([OH:7])=O.[C:12](Cl)(=[O:16])[C:13](Cl)=O.[O:18]1[CH2:22][CH2:21][NH:20][C:19]1=O.[CH2:24]([Li])[CH2:25][CH2:26][CH3:27].[CH2:29](Cl)Cl>CN(C=O)C.C1COCC1>[CH3:22][C@@H:21]1[C@H:12]([C:13]2[CH:29]=[CH:24][CH:25]=[CH:26][CH:27]=2)[O:16][C:19](=[O:18])[N:20]1[C:5](=[O:7])[CH2:4][CH2:3][C@H:2]([CH3:1])[CH2:8][CH2:9][CH2:10][CH3:11]

Komponenten

8

Edukt 5

HCID 6344DichloromethaneHCID 65578Oxalyl chlorideHCID 739492-OxazolidinoneHCID 6997333(4R)-4-methyloctanoic acidHCID 178418339Butyllithium

Produkt 1

HCID 57142278(4R,5S)-4-Methyl-3-((R)-4-methyl-octanoyl)-5-phenyl-oxazolidin-2-one

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6228DimethylformamideKatalysatorHCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

To acid 136 (2.14 g, 13.5 mmol) in 25 mL CH2Cl2 at 0° C. was added 3 drops DMF, followed by oxalyl chloride (1.42 mL, 16.2 mmol) resulting in vigorous gas evolution. The solution was warmed directly to ambient temperature, stirred 30 minutes, and concentrated. Meanwhile, to a solution of the oxazolidinone (2.64 g, 14.9 mmol) in 40 mL THF at −78° C. was added n-butyllithium (1.6 M soln in hexanes, 9.3 mL, 14.9 mmol) dropwise. The mixture was stirred for 10 minutes at which time the acid chloride in 10 mL THF was added dropwise. The reaction was stirred 30 minutes at −78° C., then warmed directly to ambient temperature and quenched with sat. NH4Cl. The mixture was partitioned between Et2O and sat. NH4Cl (aq), the phases were separated, and the organic phase dried (MgSO4), and concentrated to furnish 3.2 g of oxazolidinone 137 as a colorless oil. LRMS: m/z 318.2 (M+); 1H NMR (CDCl3): δ7.34 (m, 5H), 5.64 (d, J=7.3 Hz, 1H), 4.73 (quint, J=6.8 Hz, 1H), 2.96 (m, 1H), 2.86 (m, 1), 1.66 (m, 1H), 1.47 (m, 2H), 1.26 (m, 5H), 1.13 (m, 1H), 0.88 (m, 9H). The crude product was used without purification.

Aufarbeitung

  1. customresulting in vigorous gas evolution
  2. concentrationconcentrated
  3. additionwas added dropwise
  4. stirringThe reaction was stirred 30 minutes at −78° C.
  5. temperaturewarmed directly to ambient temperature
  6. customquenched with sat. NH4Cl
  7. customThe mixture was partitioned between Et2O and sat. NH4Cl (aq)
  8. customthe phases were separated
  9. dry with materialthe organic phase dried (MgSO4)
  10. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-2838ed836ec54e21b0894d7c6277ea34
Quelldatensatz
uspto-grants-2003_11
Patentnummer
US06642398B2

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