Allyl bromide → (S)-tert-butyl 4-((R)-2-(allyloxymethyl)pent-4-enyl)-2,2-dimethyloxazolidine-3-carboxylate

HRID 451827Notes

Reaction equation

HRID 451827 reaction equation
[OH:1][CH2:2][C@H:3]([CH2:19][CH:20]=[CH2:21])[CH2:4][C@H:5]1[CH2:9][O:8][C:7]([CH3:11])([CH3:10])[N:6]1[C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13].[H-].[Na+].[CH2:24](Br)[CH:25]=[CH2:26]>C1COCC1>[CH2:26]([O:1][CH2:2][C@H:3]([CH2:19][CH:20]=[CH2:21])[CH2:4][C@H:5]1[CH2:9][O:8][C:7]([CH3:11])([CH3:10])[N:6]1[C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[CH:25]=[CH2:24]

Participants

5

Reactant 3

HCID 7841Allyl bromideHCID 24758Sodium hydrideHCID 58011478(S)-tert-Butyl 4-((R)-2-(hydroxymethyl)pent-4-en-1-yl)-2,2-dimethyloxazolidine-3-carboxylate

Product 1

HCID 59201545(S)-tert-butyl 4-((R)-2-(allyloxymethyl)pent-4-enyl)-2,2-dimethyloxazolidine-3-carboxylateYield 77%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of (S)-tert-butyl 4-((R)-2-(hydroxymethyl)pent-4-enyl)-2,2-dimethyloxazolidine-3-carboxylate (30 g, 100 mmol, 1 eq) in anhydrous THF (600 mL) was added NaH (60%, 16 g, 400 mmol, 4 eq) in portions at 0° C. The mixture was stirred for 10 min at 0° C., followed by the dropwise addition of allyl bromide (48 g, 400 mmol, 4 eq) over 15 min. After stirring for 30 min at 0° C., the mixture was allowed to warm to rt and stirred for 16 h. The reaction was quenched with aq. NH4Cl and the mixture was extracted with EA (3×). The combined organic layers were washed with brine, dried over Na2SO4, concentrated under reduced pressure to afford the crude product. It was purified by column chromatography on silica gel (PE:EA=100:1→60:1) to give (S)-tert-butyl 4-((R)-2-(allyloxymethyl)pent-4-enyl)-2,2-dimethyloxazolidine-3-carboxylate (26.15 g, 77.0%).

Workup

  1. stirringAfter stirring for 30 min at 0° C.
  2. temperatureto warm to rt
  3. stirringstirred for 16 h
  4. customThe reaction was quenched with aq. NH4Cl
  5. extractionthe mixture was extracted with EA (3×)
  6. washThe combined organic layers were washed with brine
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated under reduced pressure
  9. customto afford the crude product
  10. customIt was purified by column chromatography on silica gel (PE:EA=100:1→60:1)

Sources & evidence

ORD record
ord-f10e1a29f33f44f49b1a8bafc58d2787
Source dataset
uspto-grants-2013_07
Patent number
US08487108B2

Reaction notes

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