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

HRID 1417616Notes

Reaction equation

HRID 1417616 reaction equation
[N:1]([C@@H:4]1[C:40]([CH3:42])([CH3:41])[C@H:39]2[C@@:7]3([O:35][C:11]4[C:12]5[CH2:13][N:14]([C:28]([O:30][C:31]([CH3:34])([CH3:33])[CH3:32])=[O:29])[C:15](=[O:27])[C:16]=5[CH:17]=[C:18]([O:19][CH2:20][C:21]5[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=5)[C:10]=4[CH2:9][C@:8]3([CH3:44])[C@@H:36]([CH3:43])[CH2:37][CH2:38]2)[CH2:6][CH2:5]1)=[N+]=[N-].O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(OCC)(=O)C>C1COCC1>[NH2:1][C@@H:4]1[C:40]([CH3:42])([CH3:41])[C@H:39]2[C@@:7]3([O:35][C:11]4[C:12]5[CH2:13][N:14]([C:28]([O:30][C:31]([CH3:34])([CH3:33])[CH3:32])=[O:29])[C:15](=[O:27])[C:16]=5[CH:17]=[C:18]([O:19][CH2:20][C:21]5[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=5)[C:10]=4[CH2:9][C@:8]3([CH3:44])[C@@H:36]([CH3:43])[CH2:37][CH2:38]2)[CH2:6][CH2:5]1

Participants

6

Reactant 4

HCID 962WaterHCID 8857Ethyl AcetateHCID 11776TriphenylphosphineHCID 86753815(6aR,7S,9aS,11S,13aS)-11-azido-5-benzyloxy-2-(t-butoxycarbonyl)-2,3,6,6a,7,8,9,9a,10,11,12,13-dodecahydro-6a,7,10,10-tetramethyl-3-oxo-1H-benzo[8,8a][1]benzopyrano[2,3-e]isoindole

Product 1

HCID 86753816(6aR,7S,9aS,11S,13aS)-11-amino-5-benzyloxy-2-(t-butoxycarbonyl)-2,3,6,6a,7,8,9,9a,10,11,12,13-dodecahydro-6a,7,10,10-tetramethyl-3-oxo-1H-benzo[8,8a][1]benzopyrano[2,3-e]isoindoleYield 91.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To the above Compound (44) (300 mg, 0.50 mmol) dissolved in 10 ml of THF were added 1.0 ml of water and 270 mg (1.03 mmol) of triphenylphosphine. The mixture was heated to reflux for 24 hours. After the addition of ethyl acetate, it was dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was loaded onto a silica gel column (silica gel 20 g), followed by elution with 60 ml of ethyl acetate to remove nonpolar fractions. The polar fractions eluted with 120 ml of ethyl acetate and 80 ml of chloroform-methanol (20:1) mixture were combined, and concentrated under reduced pressure. The residue was further purified by a column chromatography (Merck, Lobar column, size B; chloroform:methanol=20:1-10:1) to give 262 mg (83%) of Compound (45a) as a powdery material.

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux for 24 hours
  3. dry with materialwas dried over anhydrous magnesium sulfate
  4. concentrationconcentrated under reduced pressure
  5. washfollowed by elution with 60 ml of ethyl acetate
  6. customto remove nonpolar fractions
  7. washThe polar fractions eluted with 120 ml of ethyl acetate and 80 ml of chloroform-methanol (20:1) mixture
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was further purified by a column chromatography (Merck, Lobar column, size B; chloroform:methanol=20:1-10:1)

Sources & evidence

ORD record
ord-6c60654c894d4a4e80e22b961e4aa841
Source dataset
uspto-grants-1999_03
Patent number
US05876984

Reaction notes

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