Lithium iodide → 2-Cyclopenten-1-ol, 4-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-, cis-

HRID 2541

Reaktionsgleichung

Reaktionsgleichung von HRID 2541
[O:1]([CH:9]1[CH2:13][C:12](=[O:14])[CH:11]=[CH:10]1)[Si:2]([C:5]([CH3:8])([CH3:7])[CH3:6])([CH3:4])[CH3:3].[I-].[Li+].[H-].[Al+3].[Li+].[H-].[H-].[H-]>C(OCC)C>[Si:2]([O:1][C@@H:9]1[CH2:13][C@H:12]([OH:14])[CH:11]=[CH:10]1)([C:5]([CH3:8])([CH3:7])[CH3:6])([CH3:4])[CH3:3]

Komponenten

5

Edukt 3

HCID 66321Lithium iodideHCID 41316994-((tert-Butyl(dimethyl)silyl)oxy)cyclopent-2-en-1-oneHCID 21226445Aluminium lithium hydride

Produkt 1

HCID 101767472-Cyclopenten-1-ol, 4-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-, cis-Ausbeute 80 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 3283Diethyl EtherLösungsmittel

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

A mechanically stirred solution of 4-tert-butyldimethylsiloxy-2-cyclopentenone (1.01 g, 4.76 mmol) in anhydrous ethyl ether (20 mL) under an atmosphere of argon is treated with lithium iodide (3.20 g, 23.9 mmol). The mixture is cooled to -78° C. and treated with lithium aluminum hydride (184 mg, 4.85 mmol) in one portion. The reaction is then stirred for 90 minutes. It is then quenched by slow addition of aqueous sodium hydroxide (1N, 23 mL) at a rate that maintains the temperature of the reaction below 20° C. The resulting suspension is then filtered through a pad of diatomaceous earth and the pad is subsequently rinsed with ether. The filtrate phases are separated and the aqueous phase is extracted with ether (20 mL). The organic phase and organic extract are combined, rinsed with aqueous sodium hydroxide (1N, 20 mL), brine (20 mL), dried over anhydrous magnesium sulfate, filtered and concentrated under vacuum (40° C., 20 mmHg). The residue is then purified by Kugelrohr distillation (60°-80° C., 1 mmHg) to provide the title compound. (820 mg, 80% yield) as a colorless oil; cis/trans/1-2+1-4 addition, 88.5/3.3/8.2.

Aufarbeitung

  1. customIt is then quenched by slow addition of aqueous sodium hydroxide (1N, 23 mL) at a rate
  2. customthe temperature of the reaction below 20° C
  3. filtrationThe resulting suspension is then filtered through a pad of diatomaceous earth
  4. washthe pad is subsequently rinsed with ether
  5. customThe filtrate phases are separated
  6. extractionthe aqueous phase is extracted with ether (20 mL)
  7. extractionThe organic phase and organic extract
  8. washrinsed with aqueous sodium hydroxide (1N, 20 mL), brine (20 mL)
  9. dry with materialdried over anhydrous magnesium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated under vacuum (40° C., 20 mmHg)
  12. distillationThe residue is then purified by Kugelrohr distillation (60°-80° C., 1 mmHg)

Quellen und Nachweise

ORD-Eintrag
ord-3ce9d725cf794ddb8c67a20faaad2014
Quelldatensatz
uspto-grants-1998_03
Patentnummer
US05728899

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