Allyl bromide → HCID 68292782, compound

HRID 529451Notes

Reaction equation

HRID 529451 reaction equation
C[Si]([N-][Si](C)(C)C)(C)C.[Na+].[CH2:11]([C@H:18]1[CH2:22][O:21][C:20](=[O:23])[N:19]1[C:24](=[O:52])[C@@H:25]([CH2:44][C:45]1[CH:50]=[CH:49][CH:48]=[C:47]([F:51])[CH:46]=1)/[CH:26]=[CH:27]/[CH2:28][C:29]([N:31]1[C@@H:35]([CH2:36][C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)[CH2:34][O:33][C:32]1=[O:43])=[O:30])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.[CH2:53](Br)[CH:54]=[CH2:55]>C1COCC1>[CH2:55]([C@@H:28](/[CH:27]=[CH:26]/[C@H:25]([CH2:44][C:45]1[CH:50]=[CH:49][CH:48]=[C:47]([F:51])[CH:46]=1)[C:24]([N:19]1[C@@H:18]([CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[CH2:22][O:21][C:20]1=[O:23])=[O:52])[C:29]([N:31]1[C@@H:35]([CH2:36][C:37]2[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=2)[CH2:34][O:33][C:32]1=[O:43])=[O:30])[CH:54]=[CH2:53]

Participants

5

Reactant 3

HCID 7841Allyl bromideHCID 2724254Sodium bis(trimethylsilyl)amideHCID 68291963HCID 68291963, compound

Product 1

HCID 68292782HCID 68292782, compoundYield 25.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

A solution of NaHMDS (1.0 M in THF, 0.313 mL, 0.313 mmol) was slowly added dropwise over 5 min to a −78° C. solution of (S,E)-1,6-bis((S)-4-benzyl-2-oxooxazolidin-3-yl)-2-(3-fluorobenzyl)hex-3-ene-1,6-dione (170 mg, 0.298 mmol) in THF (1.6 mL). After addition the reaction mixture was allowed to stir for another 25 min at −78° C. and then allyl bromide (108 mg, 0.894 mmol) was added dropwise. The reaction temperature was then slowly raised to 0° C. over 20 min and then stirred at 0° C. for an additional 1 hr. The reaction was quenched by addition of saturated NH4Cl. The mixture was then partitioned between EtOAc and water. The organic phase was isolated, washed with saturated aqueous NaCl, dried over MgSO4 and concentrated. The crude product was purified using silica gel chromatography (ISCO system) eluting with a gradient of 0-100% EtOAc/Hex to give (2S,5S,E)-2-allyl-1,6-bis((S)-4-benzyl-2-oxooxazolidin-3-yl)-5-(3-fluorobenzyl)hex-3-ene-1,6-dione (46 mg, 0.075 mmol, 25% yield) as a foam. Anal. Calcd. for C36H35FN2O6 m/z 610.2. found: 611.0 (M+H)+.

Workup

  1. additionAfter addition the reaction mixture
  2. temperatureThe reaction temperature was then slowly raised to 0° C. over 20 min
  3. stirringstirred at 0° C. for an additional 1 hr
  4. customThe reaction was quenched by addition of saturated NH4Cl
  5. customThe mixture was then partitioned between EtOAc and water
  6. customThe organic phase was isolated
  7. washwashed with saturated aqueous NaCl
  8. dry with materialdried over MgSO4
  9. concentrationconcentrated
  10. customThe crude product was purified
  11. washeluting with a gradient of 0-100% EtOAc/Hex

Sources & evidence

ORD record
ord-348b8bafba2f4842ab0132a65cfd2551
Source dataset
uspto-grants-2016_05
Patent number
US09346852B2

Reaction notes

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