Dimethyl Sulfoxide → (S)-Tert-butyl 2,2-dimethyl-4-(2-oxoethyl)oxazolidine-3-carboxylate

HRID 19026Notes

Reaction equation

HRID 19026 reaction equation
CS(C)=O.C(Cl)(=O)C(Cl)=O.[C:11]([O:15][C:16]([N:18]1[C@@H:22]([CH2:23][CH2:24][OH:25])[CH2:21][O:20][C:19]1([CH3:27])[CH3:26])=[O:17])([CH3:14])([CH3:13])[CH3:12].C(N(CC)CC)C>ClCCl>[C:11]([O:15][C:16]([N:18]1[C@@H:22]([CH2:23][CH2:24][OH:25])[CH2:21][O:20][C:19]1([CH3:27])[CH3:26])=[O:17])([CH3:14])([CH3:13])[CH3:12].[C:11]([O:15][C:16]([N:18]1[C@@H:22]([CH2:23][CH:24]=[O:25])[CH2:21][O:20][C:19]1([CH3:27])[CH3:26])=[O:17])([CH3:14])([CH3:13])[CH3:12]

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 10847957tert-butyl (4S)-4-(2-hydroxyethyl)-2,2-dimethyl-1,3-oxazolidine-3-carboxylate

Product 2

HCID 10586317(S)-Tert-butyl 2,2-dimethyl-4-(2-oxoethyl)oxazolidine-3-carboxylateYield 201.4%HCID 10847957tert-butyl (4S)-4-(2-hydroxyethyl)-2,2-dimethyl-1,3-oxazolidine-3-carboxylate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Conditions

Temperature
-60 °C

Procedure

(S)-4-(2-Hydroxy-ethyl)-2,2-dimethyl-oxazolidine-3-carboxylic acid t-butyl ester was prepared according to the literature procedure (J. Org. Chem. 2001, 66, 206-215). A solution of dimethylsulfoxide (3.5 mL) in dichloromethane (15 mL) was added dropwise to a cooled solution (−78° C.) of oxalyl chloride (2M in dichloromethane, 13 mL) in dichloromethane (40 mL). The solution was stirred at −60° C. for 15 min before the slow addition of (S)-4-(2-hydroxy-ethyl)-2,2-dimethyl-oxazolidine-3-carboxylic acid t-butyl ester (4.5 g, 18.37 mmol) in dichloromethane (20 mL). The mixture was stirred at −60° C. for 30 min and triethylamine (13 mL) was added. After stirring for 30 min, the cooling bath was removed and the mixture was stirred for 1 h at room temperature. The mixture was extracted with dichloromethane and water. The organic layer was dried over sodium sulfate. Solvents were evaporated to give (S)-2,2-dimethyl-4-(2-oxo-ethyl)-oxazolidine-3-carboxylic acid t-butyl ester (4.50 g, 100%) as a colorless oil: 1H NMR (300 MHz, CDCl3) δ ppm 1.42-1.52 (m, 12H), 1.51, 1.63 (2×s, 3H), 2.50-3.16 (m, 2H), 3.73 (d, J=9.1 Hz, 1H), 3.99-4.16 (m, 1H), 4.22-4.44 (m, 1H), 9.79 (s, 1H).

Workup

  1. stirringAfter stirring for 30 min
  2. customthe cooling bath was removed
  3. stirringthe mixture was stirred for 1 h at room temperature
  4. extractionThe mixture was extracted with dichloromethane and water
  5. dry with materialThe organic layer was dried over sodium sulfate
  6. customSolvents were evaporated

Sources & evidence

ORD record
ord-d9b7b4237b07412d949c4da23e4d3809
Source dataset
uspto-grants-2010_06
Patent number
US07741327B2

Reaction notes

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