Allyl iodide → HCID 68292176, compound

HRID 529450Notes

Reaction equation

HRID 529450 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][C:48]([F:51])=[CH:47][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](I)[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][C:48]([F:51])=[CH:47][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:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)[CH2:34][O:33][C:32]1=[O:43])=[O:30])[CH:54]=[CH2:53]

Participants

5

Reactant 3

HCID 11166Allyl iodideHCID 2724254Sodium bis(trimethylsilyl)amideHCID 68292103HCID 68292103, compound

Product 1

HCID 68292176HCID 68292176, compoundYield 57.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

A solution of NaHMDS (1.0 M in THF, 1.34 mL, 1.34 mmol) was slowly added dropwise over 10 min to a −78° C. solution of (S,E)-1,6-bis((S)-4-benzyl-2-oxooxazolidin-3-yl)-2-(4-fluorobenzyl)hex-3-ene-1,6-dione (763 mg, 1.34 mmol) in THF (4.8 mL). After the addition, the reaction mixture was allowed to stir for another 30 min at −78° C. and then a solution of allyl iodide (225 mg, 1.34 mmol) in THF (0.5 mL) was added dropwise. The reaction temperature was then warmed to −40° C. and stirred at −40° C. for 45 min. Then the reaction was warmed to 0° C. and stirred at 0° C. for an additional 1 hr. The reaction was quenched by the 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-(4-fluorobenzyl)hex-3-ene-1,6-dione (470 mg, 0.770 mmol, 57.6% yield) as a foam. Anal. Calcd. for C36H35FN2O6 m/z 610.2. found: 611.2 (M+H)+.

Workup

  1. additionAfter the addition
  2. temperatureThe reaction temperature was then warmed to −40° C.
  3. stirringstirred at −40° C. for 45 min
  4. temperatureThen the reaction was warmed to 0° C.
  5. stirringstirred at 0° C. for an additional 1 hr
  6. customThe reaction was quenched by the addition of saturated NH4Cl
  7. customThe mixture was then partitioned between EtOAc and water
  8. customThe organic phase was isolated
  9. washwashed with saturated aqueous NaCl
  10. dry with materialdried over MgSO4
  11. concentrationconcentrated
  12. customThe crude product was purified
  13. washeluting with a gradient of 0-100% EtOAc/Hex

Sources & evidence

ORD record
ord-5eeddbb2ea43417bb085c886b32400a0
Source dataset
uspto-grants-2016_05
Patent number
US09346852B2

Reaction notes

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