Sodium hydride → Tert-butyl(+/-)-(1S,5R)-4-methylbicyclo[3.2.0]hept-3-en-6-ylideneacetate

HRID 551694Notes

Reaction equation

HRID 551694 reaction equation
[CH3:1][C:2]1[C@H:8]2[C@H:5]([CH2:6][C:7]2=O)[CH2:4][CH:3]=1.[H-].[Na+].COP([CH2:18][C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])(OC)=O>O1CCCC1>[CH3:1][C:2]1[C@H:8]2[C@H:5]([CH2:6][C:7]2=[CH:18][C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:4][CH:3]=1

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 4564495tert-Butyl DimethylphosphonoacetateHCID 11126242(+/-)-(1S,5R)-4-methylbicyclo[3.2.0]hept-3-en-6-one

Product 1

HCID 86646157Tert-butyl(+/-)-(1S,5R)-4-methylbicyclo[3.2.0]hept-3-en-6-ylideneacetate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

(±)-(1S,5R)-4-methylbicyclo[3.2.0]hept-3-en-6-one (1.10 g, 9.0 mmol) was added to a reaction solution prepared in advance by adding sodium hydride (>65% oil, 342.8 mg, 9.0 mmol) to a tetrahydrofuran solution (10 mL) of tert-butyl dimethoxyphosphorylacetate (2.08 g, 9.3 mmol) under ice cooling, and the mixture was further stirred for 2 hours. The reaction solution was separated into aqueous and organic layers by the addition of a saturated aqueous solution of ammonium chloride and saturated saline. The aqueous layer was subjected to extraction with ethyl acetate. These organic layers were combined, then washed with saturated saline, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain the compound of interest as a pale yellow oil substance (1.59 g, 80%, E/Z mixture).

Workup

  1. customprepared in advance
  2. customThe reaction solution was separated into aqueous and organic layers
  3. additionby the addition of a saturated aqueous solution of ammonium chloride and saturated saline
  4. extractionThe aqueous layer was subjected to extraction with ethyl acetate
  5. washwashed with saturated saline
  6. dry with materialdried over anhydrous magnesium sulfate
  7. distillationThe solvent was distilled off under reduced pressure
  8. customthe residue was purified by silica gel column chromatography
  9. customto obtain the compound of interest as a pale yellow oil substance (1.59 g, 80%, E/Z mixture)

Sources & evidence

ORD record
ord-36bc9744d999448bbc43565dd16265c8
Source dataset
uspto-grants-2011_05
Patent number
US07947738B2

Reaction notes

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