Triphenylphosphine → (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

HRID 1417610Notes

Reaction equation

HRID 1417610 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O.[CH2:32]([O:39][C:40]1[C:41]2[CH2:60][C@:59]3([CH3:73])[C@@H:61]([CH3:72])[CH2:62][CH2:63][C@H:64]4[C:65]([CH3:71])([CH3:70])[C@@H:66](O)[CH2:67][CH2:68][C@@:58]34[O:57][C:42]=2[C:43]2[CH2:44][N:45]([C:50]([O:52][C:53]([CH3:56])([CH3:55])[CH3:54])=[O:51])[C:46](=[O:49])[C:47]=2[CH:48]=1)[C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1>C1C=CC=CC=1>[CH2:32]([O:39][C:40]1[C:41]2[CH2:60][C@:59]3([CH3:73])[C@@H:61]([CH3:72])[CH2:62][CH2:63][C@H:64]4[C:65]([CH3:71])([CH3:70])[CH:66]=[CH:67][CH2:68][C@@:58]34[O:57][C:42]=2[C:43]2[CH2:44][N:45]([C:50]([O:52][C:53]([CH3:56])([CH3:55])[CH3:54])=[O:51])[C:46](=[O:49])[C:47]=2[CH:48]=1)[C:33]1[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=1

Participants

5

Reactant 3

HCID 11776Triphenylphosphine2×HCID 220568ethyl N-ethoxycarbonyliminocarbamate2×HCID 86753807(6aR,7S,9aS,11S,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-3-oxo-1H-benzo[8,8a][1]benzopyrano[2,3-e]isoindole

Product 1

HCID 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]isoindoleYield 89%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

Under nitrogen, 344 mg (1.31 mmol) of triphenylphosphine and 170 μl (1.08 mmol) of diethyl azodicarboxylate were added to a solution of Compound (39a) (503 mg, 0.875 mmol) in 35 ml of dry benzene, and the mixture heated to reflux for 25 min. After cooling to room temperature, the same amounts of triphenylphosphine and diethyl azodicarboxylate were added to the reaction mixture. The mixture was then heated to reflux for 25 min, and concentrated under reduced pressure to a half volume. The residue was purified by a silica gel column chromatography (silica gel 55 g; n-hexane:ethyl acetate=6:1) to give 434 mg (89%) of Compound (40a).

Workup

  1. temperaturethe mixture heated
  2. temperatureto reflux for 25 min
  3. temperatureThe mixture was then heated
  4. temperatureto reflux for 25 min
  5. concentrationconcentrated under reduced pressure to a half volume
  6. customThe residue was purified by a silica gel column chromatography (silica gel 55 g; n-hexane:ethyl acetate=6:1)

Sources & evidence

ORD record
ord-f38b535e9ecb4f048e1aca6f88a26212
Source dataset
uspto-grants-1999_03
Patent number
US05876984

Reaction notes

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