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Isopropanol → (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR 13bR)-benzyl 9-(4-(methoxycarbonyl)phenyl)-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]chrysene-3a-carboxylate

HRID 85549
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 85549
[CH3:1][C@:2]12[C@@:19]3([CH3:20])[C@@H:10]([C@:11]4([CH3:31])[C@@H:16]([CH2:17][CH2:18]3)[C:15]([CH3:22])([CH3:21])[C:14](OS(C(F)(F)F)(=O)=O)=[CH:13][CH2:12]4)[CH2:9][CH2:8][CH:7]1[C@H:6]1[C@H:32]([C:35]([CH3:37])=[CH2:36])[CH2:33][CH2:34][C@:5]1([C:38]([O:40][CH2:41][C:42]1[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=1)=[O:39])[CH2:4][CH2:3]2.CC(O)C.O.C(=O)([O-])[O-].[Na+].[Na+].[CH3:59][O:60][C:61]([C:63]1[CH:68]=[CH:67][C:66](B(O)O)=[CH:65][CH:64]=1)=[O:62]>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.O>[CH3:59][O:60][C:61]([C:63]1[CH:68]=[CH:67][C:66]([C:14]2[C:15]([CH3:22])([CH3:21])[C@H:16]3[C@:11]([CH3:31])([CH2:12][CH:13]=2)[C@@H:10]2[C@:19]([CH3:20])([C@@:2]4([CH3:1])[C@H:7]([CH2:8][CH2:9]2)[C@H:6]2[C@H:32]([C:35]([CH3:37])=[CH2:36])[CH2:33][CH2:34][C@:5]2([C:38]([O:40][CH2:41][C:42]2[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=2)=[O:39])[CH2:4][CH2:3]4)[CH2:18][CH2:17]3)=[CH:65][CH:64]=1)=[O:62]
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Komponenten

8

Edukt 4

HCID 3776IsopropanolHCID 27343694-Methoxycarbonylphenylboronic acidHCID 2735133Sodium Carbonate MonohydrateHCID 88415331(1R,3aS,5aR,5bR,7aR,11aR,11bR,13bR)-benzyl 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]chrysene-3a-carboxylate

Produkt 1

HCID 67776728
(1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR 13bR)-benzyl 9-(4-(methoxycarbonyl)phenyl)-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]chrysene-3a-carboxylate
Ausbeute 68,4 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 178418397HCID 178418397, VerbindungKatalysatorHCID 962WaterLösungsmittelHCID 312751,4-DioxaneLösungsmittel

Versuchsvorschrift

To a solution of (1R,3aS,5aR,5bR,7aR,11aR,11bR,13bR)-benzyl 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]chrysene-3a-carboxylate (6.21 g, 9.18 mmol) in dioxane (25 mL) was added 2-propanol (25 mL) and water (15 mL) followed by sodium carbonate monohydrate (3.42 g, 27.5 mmol), 4-methoxycarbonylphenylboronic acid (2.478 g, 13.77 mmol), and tetrakis(triphenylphosphine)palladium(0) (0.318 g, 0.275 mmol). The flask was attached to a reflux condenser, flushed with N2 and heated to reflux overnight. The mixture was then cooled to rt and diluted with water (75 mL). The mixture was extracted with ethyl acetate (3×75 mL) and washed with brine (75 mL). The combined organic layers were dried with MgSO4, filtered, and concentrated under reduced pressure. The residue was adsorbed to silica gel and purified by silica gel flash chromatography using a 0-20% ethyl acetate in hexanes gradient. The fractions containing the expected product were combined and concentrated under reduced pressure to give the title compound (4.16 g, 6.28 mmol, 68.4% yield) as a white foam. 1H NMR (500 MHz, CHLOROFORM-d) δ ppm 7.92 (d, J=8.24 Hz, 2H), 7.40-7.29 (m, 5H), 7.19 (d, J=8.24 Hz, 2H), 5.28 (dd, J=6.10, 1.83 Hz, 1H), 5.19-5.07 (m, 2H), 4.73 (d, J=1.83 Hz, 1H), 4.60 (s, 1H), 3.90 (s, 3H), 3.04 (td, J=10.91, 4.73 Hz, 1H), 2.20-2.32 (m, 2H), 2.09 (dd, J=17.24, 6.26 Hz, 1H), 1.95-1.82 (m, 2H), 1.69 (s, 3H), 0.97 (s, 3H), 0.95 (s, 3H), 0.92 (s, 3H), 0.91 (s, 3H), 1.75-0.87 (m, 17H), 0.82 (s, 3H).

Aufarbeitung

  1. customThe flask was attached to a reflux condenser
  2. customflushed with N2
  3. temperatureheated
  4. temperatureto reflux overnight
  5. additiondiluted with water (75 mL)
  6. extractionThe mixture was extracted with ethyl acetate (3×75 mL)
  7. washwashed with brine (75 mL)
  8. dry with materialThe combined organic layers were dried with MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure
  11. custompurified by silica gel flash chromatography
  12. additionThe fractions containing the expected product
  13. concentrationconcentrated under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-ccf7a0362a214470b404803ff7c7bfc9
Quelldatensatz
uspto-grants-2014_09
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US08846647B2

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