Methylenecyclobutane → tert-butyl (2S,3S)-2-(tert-butyldimethylsilyloxy)-5-cyclobutylidene-1-hydroxypentan-3-ylcarbamate

HRID 1921922Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1921922
[Si:1]([O:8][C@@H:9]([C@@H:12]([NH:16][C:17](=[O:23])[O:18][C:19]([CH3:22])([CH3:21])[CH3:20])[CH2:13][CH:14]=[CH2:15])[CH2:10][OH:11])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[CH2:24]=[C:25]1CC[CH2:26]1>Cl[Ru](=C1N(C2C(C)=CC(C)=CC=2C)CCN1C1C(C)=CC(C)=CC=1C)(Cl)(=CC1C=CC=CC=1)[P](C1CCCCC1)(C1CCCCC1)C1CCCCC1.ClCCCl.CCOC(C)=O>[Si:1]([O:8][C@@H:9]([C@@H:12]([NH:16][C:17](=[O:23])[O:18][C:19]([CH3:22])([CH3:21])[CH3:20])[CH2:13][CH:14]=[C:15]1[CH2:26][CH2:25][CH2:24]1)[CH2:10][OH:11])([C:4]([CH3:7])([CH3:5])[CH3:6])([CH3:3])[CH3:2]

Komponenten

6

Edukt 2

HCID 14262MethylenecyclobutaneHCID 44240485tert-butyl (2S,3S)-2-(tert-butyldimethylsilyloxy)-1-hydroxyhex-5-en-3-ylcarbamate

Produkt 1

HCID 57515834tert-butyl (2S,3S)-2-(tert-butyldimethylsilyloxy)-5-cyclobutylidene-1-hydroxypentan-3-ylcarbamateAusbeute 81 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 178425456HCID 178425456, VerbindungKatalysatorHCID 111,2-DichloroethaneLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

A solution of tert-butyl (2S,3S)-2-(tert-butyldimethylsilyloxy)-1-hydroxyhex-5-en-3-ylcarbamate (1.0 g, 2.9 mmol) and Grubbs Catalyst 2nd generation (0.12 g, 0.14 mmol) in DCE (6 mL) was treated with methylenecyclobutane (0.79 g, 12 mmol) and heated to 80° C. in a sealed vial overnight. The reaction mixture was diluted with EtOAc, washed with saturated NaHCO3 solution, and brine. The organics were dried over MgSO4 and concentrated under reduced pressure. Purification of the crude residue by column chromatography gave tert-butyl (2S,3S)-2-(tert-butyldimethylsilyloxy)-5-cyclobutylidene-1-hydroxypentan-3-ylcarbamate (0.900 g, 81% yield) as a 2:1 mixture with starting alkene.

Aufarbeitung

  1. washwashed with saturated NaHCO3 solution, and brine
  2. dry with materialThe organics were dried over MgSO4
  3. concentrationconcentrated under reduced pressure
  4. customPurification of the crude residue by column chromatography

Quellen und Nachweise

ORD-Eintrag
ord-0234e3cc27bf4b768447f0ac31d30f8a
Quelldatensatz
uspto-grants-2012_05
Patentnummer
US08173810B2

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