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

HRID 1417632Notes

Reaction equation

HRID 1417632 reaction equation
[H-].[Na+].[C:3]([O:7][C:8]([N:10]1[CH2:18][C:17]2[C:16]3[O:19][C@@:20]45[CH2:30][CH2:29][C@H:28]([OH:31])[C:27]([CH3:33])([CH3:32])[C@@H:26]4[CH2:25][CH2:24][C@H:23]([CH3:34])[C@@:21]5([CH3:35])[CH2:22][C:15]=3[C:14]([OH:36])=[CH:13][C:12]=2[C:11]1=[O:37])=[O:9])([CH3:6])([CH3:5])[CH3:4].[P:38](Cl)(=[O:53])([O:46][C:47]1[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=1)[O:39][C:40]1[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=1>CN(C)C=O>[C:3]([O:7][C:8]([N:10]1[CH2:18][C:17]2[C:16]3[O:19][C@@:20]45[CH2:30][CH2:29][C@H:28]([OH:31])[C:27]([CH3:33])([CH3:32])[C@@H:26]4[CH2:25][CH2:24][C@H:23]([CH3:34])[C@@:21]5([CH3:35])[CH2:22][C:15]=3[C:14]([O:36][P:38]([O:39][C:40]3[CH:41]=[CH:42][CH:43]=[CH:44][CH:45]=3)([O:46][C:47]3[CH:48]=[CH:49][CH:50]=[CH:51][CH:52]=3)=[O:53])=[CH:13][C:12]=2[C:11]1=[O:37])=[O:9])([CH3:4])([CH3:6])[CH3:5]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 75654Diphenyl chlorophosphateHCID 86753839(6aR,7S,9aS,11S,13aS)-2-(t-butoxycarbonyl)-2,3,6,6a,7,8,9,9a,10,11,12,13-dodecahydro-5,11-dihydroxy-6a,7,10,10-tetramethyl-3-oxo-1H-benzo[8,8a][1]benzopyrano[2,3-e]isoindole

Product 1

HCID 86753840(6aR,7S,9aS,11S,13aS)-2-(t-butoxycarbonyl)-2,3,6,6a,7,8,9,9a, 10,11,12,13-dodecahydro-11-hydroxy-6a,7,10,10-tetramethyl-3-oxo-5-diphenoxyphosphinyloxy-1H-benzo[8,8a][1]benzopyrano[2,3-e]isoindoleYield 80.4%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Under nitrogen, 40 mg (1.0 mmol) of sodium hydride (ca. 60% in oil) was added to a solution of the above Compound (55a) (234 mg, 0.48 mmol) in 2 ml of dry dimethylformamide, and the mixture stirred for 15 min. To the reaction mixture was added dropwise 120 μl (0.58 mmol) of diphenyl phosphorochloridate, and the mixture stirred for another 1.5 hours at the same temperature. After addition of ice-water under ice-cooling, the reaction 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 (silica gel 15 g; n-hexane:ethyl acetate=2:1) to give 277 mg (80%) of Compound (56a) as an oily material.

Workup

  1. stirringthe mixture stirred for another 1.5 hours at the same temperature
  2. temperaturecooling
  3. extractionthe reaction 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 (silica gel 15 g; n-hexane:ethyl acetate=2:1)

Sources & evidence

ORD record
ord-0b3dd71af41c4a07bf97cceb4d170f83
Source dataset
uspto-grants-1999_03
Patent number
US05876984

Reaction notes

Loading…