Propionyl chloride → (S)-(+)-4-Isopropyl-3-propionyl-2-oxazolidinone

HRID 1379589Notes

Reaction equation

HRID 1379589 reaction equation
[CH3:1][C@H:2](CC1CCCCC1)[C:3](Cl)=[O:4].[CH3:13][CH:14]([C@H:16]1[CH2:20][O:19][C:18](=[O:21])[NH:17]1)[CH3:15].C(Cl)(=O)CC.C([O-])(O)=O.[Na+]>C1COCC1.CCCCCC>[CH3:13][CH:14]([C@H:16]1[CH2:20][O:19][C:18](=[O:21])[N:17]1[C:3](=[O:4])[CH2:2][CH3:1])[CH3:15]

Participants

7

Reactant 4

HCID 62324Propionyl chlorideHCID 516892Sodium BicarbonateHCID 7157133(4S)-4-(propan-2-yl)-1,3-oxazolidin-2-oneHCID 10888712alpha(R)-Methylcyclohexanepropionic acid chloride

Product 1

HCID 853160(S)-(+)-4-Isopropyl-3-propionyl-2-oxazolidinoneYield 74%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

α(R)-Methylcyclohexanepropionic acid chloride: Under argon, a 1.6M hexane solution of burylithium (100 mL, 160 mmol) was added to a cooled solution (-30° to -40°) of 4(S)-(1-methylethyl)-2-oxazolidinone (20.7 g, 160 mmol), see L. N. Pridgen et al., J. Org. Chem., 54, 3231 (1989), in dry THF (200 mL). After 15 min, the mixture was cooled to -78° and propionyl chloride (14.2 mL, 163 mmol) was added. After 5 min at -78°, the reaction mixture was allowed to warm to 0°. The mixture then was treated with a saturated aqueous solution of NaHCO3 (500 mL). The resultant mixture was extracted with EtOAc (2 X). The combined organic extracts were dried (MgSO4) and concentrated to afford a yellow liquid. This material was purified by flash chromatography [SiO2, eluent: EtOAc-hexane (1:10 to 1:4)] to provide (4S)-(1-methylethyl)-3-(1-oxopropyl)-2-oxazolidinone as a clear liquid (10.9 g, 74% yield). 1H NMR (400 MHz, CDCl3) δ 4.46-4.41 (m, 1H), 4.29-4.19 (m, 2H), 3.03-2.86 (m, 2H), 2.43-2.33 (m, 1H), 1.17 (t, J=7.3 Hz, 3H), 0.92 (d, J=7 Hz, 3H), 0.88 (d, J=7 Hz, 3H).

Workup

  1. temperaturethe mixture was cooled to -78°
  2. waitAfter 5 min at -78°
  3. temperatureto warm to 0°
  4. extractionThe resultant mixture was extracted with EtOAc (2 X)
  5. dry with materialThe combined organic extracts were dried (MgSO4)
  6. concentrationconcentrated
  7. customto afford a yellow liquid
  8. customThis material was purified by flash chromatography [SiO2, eluent: EtOAc-hexane (1:10 to 1:4)]

Sources & evidence

ORD record
ord-774964ddcd8f42d49ab8fbf0665cf7dd
Source dataset
uspto-grants-1997_09
Patent number
US05672586

Reaction notes

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