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Lithium Chloride → Ethyl 5-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(benzoyloxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)isoxazole-3-carboxylate

HRID 406888
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 406888
C([Sn](CCCC)(CCCC)[C:6]1[O:10][N:9]=[C:8]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[CH:7]=1)CCC.[C:24]([O:32][CH2:33][C@:34]12[CH2:67][CH2:66][C@@H:65]([C:68]([CH3:70])=[CH2:69])[C@@H:35]1[C@@H:36]1[C@@:49]([CH3:52])([CH2:50][CH2:51]2)[C@@:48]2([CH3:53])[C@@H:39]([C@:40]3([CH3:64])[C@@H:45]([CH2:46][CH2:47]2)[C:44]([CH3:55])([CH3:54])[C:43](OS(C(F)(F)F)(=O)=O)=[CH:42][CH2:41]3)[CH2:38][CH2:37]1)(=[O:31])[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1.[Cl-].[Li+]>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:24]([O:32][CH2:33][C@:34]12[CH2:67][CH2:66][C@@H:65]([C:68]([CH3:70])=[CH2:69])[C@@H:35]1[C@@H:36]1[C@@:49]([CH3:52])([CH2:50][CH2:51]2)[C@@:48]2([CH3:53])[C@@H:39]([C@:40]3([CH3:64])[C@@H:45]([CH2:46][CH2:47]2)[C:44]([CH3:54])([CH3:55])[C:43]([C:6]2[O:10][N:9]=[C:8]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[CH:7]=2)=[CH:42][CH2:41]3)[CH2:38][CH2:37]1)(=[O:31])[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1
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Komponenten

6

Edukt 3

HCID 433294Lithium ChlorideHCID 2763256Ethyl 5-(tributylstannyl)-1,2-oxazole-3-carboxylateHCID 86666260((1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-9-(trifluoromethylsulfonyloxy)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-3a-yl)methyl benzoate

Produkt 1

HCID 67777149
Ethyl 5-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(benzoyloxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)isoxazole-3-carboxylate
Ausbeute 20,3 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178418397HCID 178418397, VerbindungKatalysatorHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
85 °C

Versuchsvorschrift

To a sealable vial containing ethyl 5-(tributylstannyl)isoxazole-3-carboxylate (0.052 g, 0.122 mmol) was added ((1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-9-(trifluoromethylsulfonyloxy)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-3a-yl)methyl benzoate (0.075 g, 0.111 mmol), lithium chloride (0.014 g, 0.332 mmol), and tetrakis(triphenylphosphine)palladium(0) (6.40 mg, 5.54 μmol). The mixture was diluted with 1,4-Dioxane (2 mL) and was flushed with N2. The vial was sealed and heated to 85° C. After 15.5 h of heating, the mixture was cooled to rt, was diluted with water (4 mL), and was extracted with dichloromethane (3×4 mL). The combined organic layers were dried over Na2SO4. The drying agent was removed by filtration and the filtrate was concentrated under reduced pressure. The residue was purified by Biotage flash chromatography using a 0-10% EtOAc in hexanes gradient. The fractions containing the expected product were combined and concentrated under reduced pressure. Ethyl 5-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(benzoyloxymethyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)isoxazole-3-carboxylate was isolated as an off-white foam (0.015 g total mass, 0.022 mmol, 20.3% yield). LCMS: m/e 668.53 (M+H)+, 3.11 min (method 1).

Aufarbeitung

  1. customwas flushed with N2
  2. customThe vial was sealed
  3. temperatureAfter 15.5 h of heating
  4. temperaturethe mixture was cooled to rt
  5. additionwas diluted with water (4 mL)
  6. extractionwas extracted with dichloromethane (3×4 mL)
  7. dry with materialThe combined organic layers were dried over Na2SO4
  8. customThe drying agent was removed by filtration
  9. concentrationthe filtrate was concentrated under reduced pressure
  10. customThe residue was purified by Biotage flash chromatography
  11. additionThe fractions containing the expected product
  12. concentrationconcentrated under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-ca74c13023ec4048a979d625329b9c0d
Quelldatensatz
uspto-grants-2014_06
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US08754068B2

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