Trimethylamine oxide dihydrate → (6aR,7S,9aS,11R,12S,13aS)-5-benzyloxy-2-(t-butoxycarbonyl)-2,3,6,6a,7,8,9,9a,10,11,12,13-dodecahydro-11,12-dihydroxy-6a,7,10,10-tetramethyl-3-oxo-1H-benzo[8,8a][1]benzopyrano[2,3-e]isoindole

HRID 1417621Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1417621
[CH2:1]([O:8][C:9]1[C:10]2[CH2:29][C@:28]3([CH3:41])[C@@H:30]([CH3:40])[CH2:31][CH2:32][C@H:33]4[C:34]([CH3:39])([CH3:38])[CH:35]=[CH:36][CH2:37][C@@:27]34[O:26][C:11]=2[C:12]2[CH2:13][N:14]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[C:15](=[O:18])[C:16]=2[CH:17]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[OH2:42].[OH2:43].C[N+]([O-])(C)C.C(=O)([O-])O.[Na+].S([O-])(O)=O.[Na+]>CC(C)=O.[Os](=O)(=O)(=O)=O.O>[CH2:1]([O:8][C:9]1[C:10]2[CH2:29][C@:28]3([CH3:41])[C@@H:30]([CH3:40])[CH2:31][CH2:32][C@H:33]4[C:34]([CH3:39])([CH3:38])[C@@H:35]([OH:43])[C@@H:36]([OH:42])[CH2:37][C@@:27]34[O:26][C:11]=2[C:12]2[CH2:13][N:14]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[C:15](=[O:18])[C:16]=2[CH:17]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Komponenten

8

Edukt 4

HCID 198430Trimethylamine oxide dihydrate2×HCID 516892Sodium BicarbonateHCID 23665763Sodium BisulfiteHCID 86753806(6aR,7S,9aS,13aS)-5-benzyloxy-2-(t-butoxycarbonyl)-2,3,6,6a,7,8,9,9a,10,13-decahydro-6a,7,10,10-tetramethyl-3-oxo-1H-benzo[8,8a][1]benzopyrano[2,3-e]isoindole

Produkt 1

HCID 86753824(6aR,7S,9aS,11R,12S,13aS)-5-benzyloxy-2-(t-butoxycarbonyl)-2,3,6,6a,7,8,9,9a,10,11,12,13-dodecahydro-11,12-dihydroxy-6a,7,10,10-tetramethyl-3-oxo-1H-benzo[8,8a][1]benzopyrano[2,3-e]isoindoleAusbeute 66 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 30318Osmium TetroxideKatalysatorHCID 180AcetoneLösungsmittelHCID 962WaterLösungsmittel

Versuchsvorschrift

To a solution of Compound (40a) (Step-2 in Example 44) (40 mg, 0.072 mmol) in 2.0 ml of acetone were added 12 mg (0.108 mmol) of trimethylamine oxide dihydrate and 0.50 ml (0.1 mmol) of 0.2M osmium tetroxide aqueous solution, and the mixture stirred at room temperature for 15 hours. After addition of 8 mg (0.072 mmol) of trimethylamine oxide dihydrate, the mixture was stirred for 5 hours. To the reaction mixture were added 236 mg (2.8 mmol) of sodium hydrogen carbonate and 146 mg (1.4 mmol) of sodium hydrogen sulfite, and the mixture stirred for 1.5 hours. After addition of water, the mixture was extracted with ethyl acetate. The extract was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by a column chromatography (Merck, Lobar column, size A; n-hexane:ethyl acetate=2:1) to give 28 mg (66%) of Compound (48a).

Aufarbeitung

  1. stirringthe mixture was stirred for 5 hours
  2. stirringthe mixture stirred for 1.5 hours
  3. extractionthe mixture was extracted with ethyl acetate
  4. washThe extract was washed with water and saturated brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by a column chromatography (Merck, Lobar column, size A

Quellen und Nachweise

ORD-Eintrag
ord-21a1eba83d3e48fcbf7b7dceb3f80e19
Quelldatensatz
uspto-grants-1999_03
Patentnummer
US05876984

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