Water → (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-hydroxy-6a,7,10,10-tetramethyl-12-(4-nitrophenylsulfonyl)oxy-3-oxo-1H-benzo[8,8a][l]-benzopyrano[2,3-e]isoindole

HRID 1417625Notes

Reaction equation

HRID 1417625 reaction equation
[CH2:1]([O:8][C:9]1[C:10]2[CH2:29][C@:28]3([CH3:43])[C@@H:30]([CH3:42])[CH2:31][CH2:32][C@H:33]4[C:34]([CH3:41])([CH3:40])[C@@H:35]([OH:39])[C@@H:36]([OH:38])[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.CN(C1C=CC=CN=1)C.[N+:53]([C:56]1[CH:61]=[CH:60][C:59]([S:62](Cl)(=[O:64])=[O:63])=[CH:58][CH:57]=1)([O-:55])=[O:54].O>ClCCl>[CH2:1]([O:8][C:9]1[C:10]2[CH2:29][C@:28]3([CH3:43])[C@@H:30]([CH3:42])[CH2:31][CH2:32][C@H:33]4[C:34]([CH3:41])([CH3:40])[C@@H:35]([OH:39])[C@@H:36]([O:38][S:62]([C:59]5[CH:58]=[CH:57][C:56]([N+:53]([O-:55])=[O:54])=[CH:61][CH:60]=5)(=[O:63])=[O:64])[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

Participants

6

Reactant 4

HCID 962WaterHCID 74044-Nitrobenzenesulfonyl chlorideHCID 218852-DimethylaminopyridineHCID 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]isoindole

Product 1

HCID 86753832(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-hydroxy-6a,7,10,10-tetramethyl-12-(4-nitrophenylsulfonyl)oxy-3-oxo-1H-benzo[8,8a][l]-benzopyrano[2,3-e]isoindoleYield 70%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of Compound (48a) (200 mg, 0.34 mmol) in 15 ml of dichloromethane were added 83 mg (0.68 mmol) of dimethylaminopyridine and 112 mg (0.51 mmol) of p-nitrobenzenesulfonyl chloride under ice-cooling, and the mixture stirred for 6 hours at the same temperature. After addition of water, the reaction mixture was extracted with ethyl acetate. The extract was washed sequentially with 1N HCl, water, an aqueous saturated sodium hydrogen carbonate solution, and water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by a column chromatography (Merck, Lobar column, size B; toluene:ethyl acetate=4:1) to give 184 mg (70%) of Compound (48f).

Workup

  1. temperaturecooling
  2. extractionthe reaction mixture was extracted with ethyl acetate
  3. washThe extract was washed sequentially with 1N HCl, water
  4. dry with materialan aqueous saturated sodium hydrogen carbonate solution, and water, dried over anhydrous sodium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was purified by a column chromatography (Merck, Lobar column, size B; toluene:ethyl acetate=4:1)

Sources & evidence

ORD record
ord-14f03627e088490f9b03d0c363855c69
Source dataset
uspto-grants-1999_03
Patent number
US05876984

Reaction notes

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