Triphenylphosphine → (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

HRID 1417615Notes

Reaction equation

HRID 1417615 reaction equation
[CH2:1]([O:8][C:9]1[C:10]2[CH2:29][C@:28]3([CH3:42])[C@@H:30]([CH3:41])[CH2:31][CH2:32][C@H:33]4[C:34]([CH3:40])([CH3:39])[C:35](=O)[CH2:36][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.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[NH:62]=[N+:63]=[N-:64].C1C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>C1C=CC=CC=1>[N:62]([C@@H:35]1[C:34]([CH3:39])([CH3:40])[C@H:33]2[C@@:27]3([O:26][C:11]4[C:12]5[CH2:13][N:14]([C:19]([O:21][C:22]([CH3:23])([CH3:25])[CH3:24])=[O:20])[C:15](=[O:18])[C:16]=5[CH:17]=[C:9]([O:8][CH2:1][C:2]5[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=5)[C:10]=4[CH2:29][C@:28]3([CH3:42])[C@@H:30]([CH3:41])[CH2:31][CH2:32]2)[CH2:37][CH2:36]1)=[N+:63]=[N-:64]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 70291861Hydrazoic acid benzeneHCID 86753805(6aR,7S,9aS,13aS)-5-benzyloxy-2-(t-butoxycarbonyl)-2,3,6,6a,7,8,9,9a,10,11,12,13-dodecahydro-6a,7,10,10-tetramethyl-3, 11-dioxo-1H-benzo[8,8a][1]benzopyrano[2,3-e]isoindole

Product 1

HCID 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]isoindoleYield 66%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

To a solution of Compound (38a) (Step-3 in Example 42) (690 mg, 1.20 mmol) in 35 ml of dry benzene were added dropwise 480 mg (1.83 mmol) of triphenylphosphine and 1.0 ml (1.88 mmol) of 1.9M hydrazoic acid/benzene solution at room temperature with stirring, followed by the addition of 290 μl (1.84 mmol) of diethyl azodicarboxylate and stirring at 80° C. for 20 min. After cooling to room temperature, the solvent was evaporated under reduced pressure. The residue was purified by a column chromatography (Merck, Lobar column, size C; toluene:ethyl acetate=9:1) to give 474 mg (66%) of Compound (44).

Workup

  1. stirringstirring at 80° C. for 20 min
  2. customthe solvent was evaporated under reduced pressure
  3. customThe residue was purified by a column chromatography (Merck, Lobar column, size C; toluene:ethyl acetate=9:1)

Sources & evidence

ORD record
ord-3ecbea0d41984025b177c66373bccea2
Source dataset
uspto-grants-1999_03
Patent number
US05876984

Reaction notes

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