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(z)-7-{(1r,2s)-2-[(e)-(s)-5-(4-Bromo-5-methyl-thiophen-2-yl)-3-(tert-butyl-dimethyl-silanyloxy)-pent-1-enyl]-5-oxo-cyclopent-3-enyl}-hept-5-enoic acid methyl ester → (z)-7-{(1r,2r)-2-[(e)-(s)-5-(4-Bromo-5-methyl-thiophen-2-yl)-3-(tert-butyl-dimethyl-silanyloxy)-pent-1-enyl]-5-oxo-cyclopentyl}-hept-5-enoic acid methyl ester

HRID 2212121
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 2212121
[CH3:1][O:2][C:3](=[O:36])[CH2:4][CH2:5][CH2:6]/[CH:7]=[CH:8]\[CH2:9][C@H:10]1[C:14](=[O:15])[CH:13]=[CH:12][C@@H:11]1/[CH:16]=[CH:17]/[C@@H:18]([O:28][Si:29]([C:32]([CH3:35])([CH3:34])[CH3:33])([CH3:31])[CH3:30])[CH2:19][CH2:20][C:21]1[S:22][C:23]([CH3:27])=[C:24]([Br:26])[CH:25]=1>C1(C)C=CC=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu].[Cu].[Cu].[Cu].[Cu].[Cu]>[CH3:1][O:2][C:3](=[O:36])[CH2:4][CH2:5][CH2:6]/[CH:7]=[CH:8]\[CH2:9][C@H:10]1[C:14](=[O:15])[CH2:13][CH2:12][C@@H:11]1/[CH:16]=[CH:17]/[C@@H:18]([O:28][Si:29]([C:32]([CH3:34])([CH3:33])[CH3:35])([CH3:30])[CH3:31])[CH2:19][CH2:20][C:21]1[S:22][C:23]([CH3:27])=[C:24]([Br:26])[CH:25]=1
KomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

4

Edukt 1

HCID 16655598(z)-7-{(1r,2s)-2-[(e)-(s)-5-(4-Bromo-5-methyl-thiophen-2-yl)-3-(tert-butyl-dimethyl-silanyloxy)-pent-1-enyl]-5-oxo-cyclopent-3-enyl}-hept-5-enoic acid methyl ester

Produkt 1

HCID 67092649(z)-7-{(1r,2r)-2-[(e)-(s)-5-(4-Bromo-5-methyl-thiophen-2-yl)-3-(tert-butyl-dimethyl-silanyloxy)-pent-1-enyl]-5-oxo-cyclopentyl}-hept-5-enoic acid methyl esterAusbeute 89,3 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 11982471
Stryker's reagent
Katalysator
HCID 1140TolueneLösungsmittel2×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

A solution of 7 (170 mg, 0.28 mmol) in 4 mL toluene was added, by cannula, to a −40° C. mixture of hydrido(triphenylphosphine)copper(I) hexamer (300 mg, 0.15 mmol) in 4 mL toluene, rinsing with 0.5 mL toluene. The temperature was allowed to warm to 0° C. over 1 h and then was allowed to warm to room temperature. After a further 1 h, the reaction was quenched by addition of 15 mL saturated NH4Cl solution. The mixture was extracted with ethyl acetate (3×15 mL) and the combined ethyl acetate solution dried (Na2SO4), filtered and evaporated. Purification by flash chromatography (8% ethyl acetate/hexanes to 10%) gave the title ketone (150 mg, 0.25 mmol, 89%).

Aufarbeitung

  1. washrinsing with 0.5 mL toluene
  2. temperatureto warm to room temperature
  3. customthe reaction was quenched by addition of 15 mL saturated NH4Cl solution
  4. extractionThe mixture was extracted with ethyl acetate (3×15 mL)
  5. dry with materialthe combined ethyl acetate solution dried (Na2SO4)
  6. filtrationfiltered
  7. customevaporated
  8. customPurification by flash chromatography (8% ethyl acetate/hexanes to 10%)

Quellen und Nachweise

ORD-Eintrag
ord-aa3db79c7e0e47e5b47fd9ff68375c27
Quelldatensatz
uspto-grants-2006_09
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US07101904B2

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