Allyl bromide → (S)-4-(2-allyloxy-pent-4-enyl)-2,2-dimethyl-oxazolidine-3-carboxylic acid t-butyl ester

HRID 19028

Reaction equation

HRID 19028 reaction equation
[C:1]([O:5][C:6]([N:8]1[C@@H:12]([CH2:13][CH:14]([OH:18])[CH2:15][CH:16]=[CH2:17])[CH2:11][O:10][C:9]1([CH3:20])[CH3:19])=[O:7])([CH3:4])([CH3:3])[CH3:2].[H-].[Na+].[CH2:23](Br)[CH:24]=[CH2:25]>O1CCCC1>[C:1]([O:5][C:6]([N:8]1[C@@H:12]([CH2:13][CH:14]([O:18][CH2:25][CH:24]=[CH2:23])[CH2:15][CH:16]=[CH2:17])[CH2:11][O:10][C:9]1([CH3:20])[CH3:19])=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 7841Allyl bromideHCID 24758Sodium hydrideHCID 59344945(S)-4-(2-hydroxy-pent-4-enyl)-2,2-dimethyl-oxazolidine-3-carboxylic acid tert-butyl ester

Product 1

HCID 59344939(S)-4-(2-allyloxy-pent-4-enyl)-2,2-dimethyl-oxazolidine-3-carboxylic acid t-butyl esterYield 48%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

(S)-4-(2-Hydroxy-pent-4-enyl)-2,2-dimethyl-oxazolidine-3-carboxylic acid tert-butyl ester (2.54 g, 8.91 mmol) was dissolved in dry tetrahydrofuran (60 mL). Sodium hydride (60% suspension in mineral oil, 360 mg) was added. The mixture was stirred at 0° C. for 5 min. Then allylbromide (1.60 mL) was added. The mixture was stirred at room temperature for 18 h. Solvents were evaporated and the residue was extracted with diethyl ether and citric acid solution. The organic layer was washed with saturated sodium chloride solution and concentrated. The crude material was purified through flash column chromatography (silica gel, 5-30% ethyl acetate/hexanes) to afford (S)-4-(2-allyloxy-pent-4-enyl)-2,2-dimethyl-oxazolidine-3-carboxylic acid t-butyl ester (1.38 g, 48% yield for two steps) as an oil: 1H NMR (300 MHz, CDCl3) δ ppm 1.48 (s, 12H), 1.56, 1.60 (2×s, 3H), 1.64-1.77 (m, 1H), 1.80-2.07 (m, 1H), 2.32 (br. s., 2H), 3.48 (br. s., 1H), 3.79-4.23 (m, 5H), 4.98-5.19 (m, 3H), 5.26 (d, J=17.2 Hz, 1H), 5.72-5.98 (m, 2H).

Workup

  1. stirringThe mixture was stirred at room temperature for 18 h
  2. customSolvents were evaporated
  3. extractionthe residue was extracted with diethyl ether and citric acid solution
  4. washThe organic layer was washed with saturated sodium chloride solution
  5. concentrationconcentrated
  6. customThe crude material was purified through flash column chromatography (silica gel, 5-30% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-97ccc01948ed4c0bacb054209452f9af
Source dataset
uspto-grants-2010_06
Patent number
US07741327B2

Linked notes

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