Chlorotrimethylsilane → HCID 86722957, compound

HRID 1404353Notes

Reaction equation

HRID 1404353 reaction equation
C[Si](Cl)(C)C.Br[CH2:7][C:8]([O:10][CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)=[O:9].C1O[C:21]2([CH2:26][CH2:25][C:24](=[O:27])[CH2:23][CH2:22]2)[O:20]C1>C(OCC)C.[Zn]>[CH2:11]([O:10][C:8](=[O:9])[CH2:7][C:24]1([OH:27])[CH2:25][CH2:26][C:21](=[O:20])[CH2:22][CH2:23]1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

Participants

6

Reactant 3

HCID 6397ChlorotrimethylsilaneHCID 62576Benzyl bromoacetateHCID 5674151,4-Dioxaspiro[4.5]decan-8-one

Product 1

HCID 86722957HCID 86722957, compoundYield 54.3%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 3283Diethyl EtherSolvent

Procedure

To a suspension of zinc dust (2.06 g, 31.5 mmol) in diethyl ether (50 mL) under argon was added trimethylsilyl chloride (3.0 mL, 23.6 mmol) and the reaction stirred for 15 min at RT. The reaction was then heated at reflux for 25 min. Benzyl bromoacetate (3.9 mL, 24.6 mmol) and 1,4-cyclohexanedione monoethylene acetal (3.05 g, 19.6 mmol) were added and the reaction was kept at reflux for 1.3 hr. The reaction was then cooled to RT, quenched with 1N HCl (125 mL) and stirred overnight. The aqueous layer was extracted with Et2O (3×). The combined organic layers were washed with sat. NaHCO3, dried over MgSO4, filtered, and concentrated. The crude product was purified by flash chromatography on silica gel (0-60% EtOAc:Hexane) to provide 2.79 g (54%) of pure product. ESI-MS m/z 285 (M+Na)+.

Workup

  1. temperatureThe reaction was then heated
  2. temperatureat reflux for 25 min
  3. temperatureat reflux for 1.3 hr
  4. temperatureThe reaction was then cooled to RT
  5. customquenched with 1N HCl (125 mL)
  6. stirringstirred overnight
  7. extractionThe aqueous layer was extracted with Et2O (3×)
  8. washThe combined organic layers were washed with sat. NaHCO3
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customThe crude product was purified by flash chromatography on silica gel (0-60% EtOAc:Hexane)

Sources & evidence

ORD record
ord-bbec0f0586824b5eab8e75fd750f6b2a
Source dataset
uspto-grants-2014_12
Patent number
US08912169B2

Reaction notes

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