Imidazole → 12-[4-deoxy-6-O-(tert-butyldiphenylsilyl)-2-O-benzyl-beta-D-glucopyranosyl]-2,3,9,10-tetrafluoro-12,13-dihydro-5H-indolo[2,3-a]pyrrolo [3,4-c]carbazole-5,7(6H)-dione

HRID 23868Notes

Reaction equation

HRID 23868 reaction equation
[CH2:1]([O:8][C@@H:9]1[C@@H:14]([OH:15])[CH2:13][C@@H:12]([CH2:16][OH:17])[O:11][C@H:10]1[N:18]1[C:30]2[C:29]3[NH:31][C:32]4[CH:33]=[C:34]([F:39])[C:35]([F:38])=[CH:36][C:37]=4[C:28]=3[C:27]3[C:40](=[O:44])[NH:41][C:42](=[O:43])[C:26]=3[C:25]=2[C:24]2[C:19]1=[CH:20][C:21]([F:46])=[C:22]([F:45])[CH:23]=2)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Si:47](Cl)([C:60]([CH3:63])([CH3:62])[CH3:61])([C:54]1[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=1)[C:48]1[CH:53]=[CH:52][CH:51]=[CH:50][CH:49]=1.N1C=CN=C1>CN(C=O)C.C(OCC)(=O)C>[Si:47]([O:17][CH2:16][C@H:12]1[O:11][C@@H:10]([N:18]2[C:30]3[C:29]4[NH:31][C:32]5[CH:33]=[C:34]([F:39])[C:35]([F:38])=[CH:36][C:37]=5[C:28]=4[C:27]4[C:40](=[O:44])[NH:41][C:42](=[O:43])[C:26]=4[C:25]=3[C:24]3[C:19]2=[CH:20][C:21]([F:46])=[C:22]([F:45])[CH:23]=3)[C@H:9]([O:8][CH2:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)[C@@H:14]([OH:15])[CH2:13]1)([C:60]([CH3:63])([CH3:62])[CH3:61])([C:54]1[CH:55]=[CH:56][CH:57]=[CH:58][CH:59]=1)[C:48]1[CH:53]=[CH:52][CH:51]=[CH:50][CH:49]=1

Participants

6

Reactant 3

HCID 795Imidazole2×HCID 94078tert-Butyldiphenylchlorosilane2×HCID 2075862212-[4-deoxy-2-O-benzyl-beta-D-glucopyranosyl]-2,3,9,10-tetrafluoro-12,13-dihydro-5H-indolo-[2,3-a]pyrrolo[3,4-c]carbazole-5,7(6H)-dione

Product 1

HCID 8675960112-[4-deoxy-6-O-(tert-butyldiphenylsilyl)-2-O-benzyl-beta-D-glucopyranosyl]-2,3,9,10-tetrafluoro-12,13-dihydro-5H-indolo[2,3-a]pyrrolo [3,4-c]carbazole-5,7(6H)-dioneYield 69%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 12-[4-deoxy-2-O-benzyl-β-D-glucopyranosyl]-2,3,9,10-tetrafluoro-12,13-dihydro-5H-indolo-[2,3-a]pyrrolo[3,4-c]carbazole-5,7(6H)-dione (0.500 g, 0.79 mmol) in 6 mL of dry DMF, at 5° C. under Ar, was added tert-butyldiphenylsilyl chloride (0.205 mL, 0.79 mmol) and imidazole (0.161 g, 2.37 mmol). After stirring this mixture at room temperature for 20 h it was re-cooled at 5° C. and more tert-butyldiphenylsilyl chloride (0.205 mL, 0.79 mmol) and imidazole (0.161 g, 2.37 mmol) were added. The resulting mixture was stirred at room temperature for 2.5 h and then it was diluted with ethyl acetate, washed (1M NaHCO3, brine), dried (MgSO4) and evaporated. Chromatography (SiO2/20-35% ethyl acetate-hexane) of the residue afforded 12-[4-deoxy-6-O-(tert-butyldiphenylsilyl)-2-O-benzyl-β-D-glucopyranosyl]-2,3,9,10-tetrafluoro-12,13-dihydro-5H-indolo[2,3-a]pyrrolo [3,4-c]carbazole-5,7(6H)-dione (0.474 g, 69%); MS (ESI−) m/e 870 (M−H)−. To a solution of a portion (0.050 g, 0.057 mmol) of this material in 2 mL of dichloromethane was added a suspension of Dess-Martin periodinane (0.048 g, 0.114 mmol) in 3 mL of dichloromethane and the mixture was stirred for 30 min. The mixture was then diluted with ethyl acetate, washed (cold 30% aq. Na2S2O3,1M NaHCO3, H2O, brine), dried (MgSO4) and evaporated. Prep tlc (SiO2/ethyl acetate-hexane, 2:3) of the residue afforded 12-[4-deoxy-6-O-(tert-butyldiphenylsilyl)-2-O-benzyl-3-oxo-β-D-glucopyranosyl]-2,3,9,10-tetrafluoro-12,13-dihydro-5H-indolo[2,3-a]pyrrolo[3,4-c]carbazole-5,7(6H)-dione (0.035 g, 70%) as a gum which solidified on standing; MS (ESI−) m/e 868 (M−H)−.

Workup

  1. temperaturewas re-cooled at 5° C.
  2. stirringThe resulting mixture was stirred at room temperature for 2.5 h
  3. washwashed (1M NaHCO3, brine)
  4. dry with materialdried (MgSO4)
  5. customevaporated

Sources & evidence

ORD record
ord-19f460827cc546b0bf8461de2c844ce7
Source dataset
uspto-grants-2005_02
Patent number
US06855698B2

Reaction notes

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