Ethyl diazoacetate → Ethyl 3-{[tert-butyl(dimethyl)silyl]oxy}bicyclo[3.1.0]hexane-6-carboxylate

HRID 1039967

Reaktionsgleichung

Reaktionsgleichung von HRID 1039967
[C:1]([Si:5]([O:8][CH:9]1[CH2:13][CH:12]=[CH:11][CH2:10]1)([CH3:7])[CH3:6])([CH3:4])([CH3:3])[CH3:2].[N+](=[CH:16][C:17]([O:19][CH2:20][CH3:21])=[O:18])=[N-]>CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.[Rh+2].[Rh+2]>[Si:5]([O:8][CH:9]1[CH2:13][CH:12]2[CH:11]([CH:16]2[C:17]([O:19][CH2:20][CH3:21])=[O:18])[CH2:10]1)([C:1]([CH3:4])([CH3:2])[CH3:3])([CH3:7])[CH3:6]

Komponenten

4

Edukt 2

HCID 12192Ethyl diazoacetateHCID 11106335Tert-butyl(cyclopent-3-en-1-yloxy)dimethylsilane

Produkt 1

HCID 67432091Ethyl 3-{[tert-butyl(dimethyl)silyl]oxy}bicyclo[3.1.0]hexane-6-carboxylateAusbeute 73 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 152122Dirhodium tetraacetateKatalysator

Versuchsvorschrift

To a flask was added tert-butyl(cyclopent-3-en-1-yloxy)dimethylsilane (0.5 g, 2.52 mmol) and rhodium(II) acetate dimer (22 mg, 0.05 mmol). The flask was evacuated and purged 5 times with argon. Dichloromethane (8.4 mL) was added and the flask was evacuated and purged 5 times with argon. In a separate flask, ethyl diazoacetate (0.37 mL, 3.02 mmol) was added. The flask was evacuated and purged with argon five times. Dichloromethane (8.4 mL) was added and the solution was added to the first flask via syringe pump over a six hour time period and then allowed to stir overnight. The mixture was filtered over a pad of celite and then concentrated. Flash chromatography was used for purification to yield ethyl 3-{[tert-butyl(dimethyl)silyl]oxy}bicyclo[3.1.0]hexane-6-carboxylate (524 mg, 1.84 mmol, 73% yield). 1H NMR (500 MHz, CDCl3) δ 4.13-4.03 (m, 2H), 2.37-2.20 (m, 1H), 2.20-2.12 (m, 1H), 2.11-1.96 (m, 1H), 1.94-1.70 (m, 4H), 1.35-1.14 (m, 4H), 0.89-0.79 (m, 9H), 0.05-−0.11 (m, 6H).

Aufarbeitung

  1. customThe flask was evacuated
  2. custompurged 5 times with argon
  3. additionDichloromethane (8.4 mL) was added
  4. customthe flask was evacuated
  5. custompurged 5 times with argon
  6. customThe flask was evacuated
  7. custompurged with argon five times
  8. additionDichloromethane (8.4 mL) was added
  9. additionthe solution was added to the first flask via syringe pump over a six hour time period
  10. filtrationThe mixture was filtered over a pad of celite
  11. concentrationconcentrated
  12. customFlash chromatography was used for purification

Quellen und Nachweise

ORD-Eintrag
ord-09d7558bbcad488f8404b748a15b9211
Quelldatensatz
uspto-grants-2013_10
Patentnummer
US08551984B2

Verknüpfte Notizen

Wird geladen…