Water → HCID 86614391, compound

HRID 2223966Notes

Reaction equation

HRID 2223966 reaction equation
CS(O[CH2:6][CH2:7][CH2:8][N:9]1[C:13]2=[N:14][CH:15]=[CH:16][C:17]([CH2:18][CH2:19][C:20]3[CH:25]=[CH:24][C:23]([O:26][C:27](=[O:32])[C:28]([CH3:31])([CH3:30])[CH3:29])=[CH:22][CH:21]=3)=[C:12]2[C:11]([O:33][C@@H:34]2[O:60][C@H:59]([CH2:61][O:62][C:63](=[O:68])[C:64]([CH3:67])([CH3:66])[CH3:65])[C@@H:51]([O:52][C:53](=[O:58])[C:54]([CH3:57])([CH3:56])[CH3:55])[C@H:43]([O:44][C:45](=[O:50])[C:46]([CH3:49])([CH3:48])[CH3:47])[C@H:35]2[O:36][C:37](=[O:42])[C:38]([CH3:41])([CH3:40])[CH3:39])=[N:10]1)(=O)=O.[N-:69]=[N+:70]=[N-:71].[Na+].O>CN(C)C=O>[N:69]([CH2:6][CH2:7][CH2:8][N:9]1[C:13]2=[N:14][CH:15]=[CH:16][C:17]([CH2:18][CH2:19][C:20]3[CH:25]=[CH:24][C:23]([O:26][C:27](=[O:32])[C:28]([CH3:31])([CH3:30])[CH3:29])=[CH:22][CH:21]=3)=[C:12]2[C:11]([O:33][C@@H:34]2[O:60][C@H:59]([CH2:61][O:62][C:63](=[O:68])[C:64]([CH3:67])([CH3:66])[CH3:65])[C@@H:51]([O:52][C:53](=[O:58])[C:54]([CH3:57])([CH3:56])[CH3:55])[C@H:43]([O:44][C:45](=[O:50])[C:46]([CH3:47])([CH3:48])[CH3:49])[C@H:35]2[O:36][C:37](=[O:42])[C:38]([CH3:39])([CH3:40])[CH3:41])=[N:10]1)=[N+:70]=[N-:71]

Participants

5

Reactant 3

HCID 962WaterHCID 33557Sodium AzideHCID 86614392HCID 86614392, compound

Product 1

HCID 86614391HCID 86614391, compoundYield 62.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of 1-(3-hydroxypropyl)-3-(2,3,4,6-tetra-pivaloyl-β-D-glucopyranosyloxy)-4-[2-(4-pivaloyloxy-phenyl)ethyl]-1H-pyrazolo[3,4-b]pyridine (0.49 g) and triethylamine (0.11 mL) in dichloromethane (5 mL) was added methanesulfonyl chloride (0.051 mL), and the mixture was stirred at room temperature for 30 minutes. The reaction mixture was poured into 0.5 mol/L hydrochloric acid, and the resulting mixture was extracted with ethyl acetate. The extract was washed with water and brine, and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to give 1-(3-methanesulfonyloxypropyl)-3-(2,3,4,6-tetra-O-pivaloyl-β-D-glucopyranosyloxy)-4-[2-(4-pivaloyloxyphenyl)ethyl]-1H-pyrazolo[3,4-b]pyridine (0.53 g). To a solution of the obtained 1-(3-methanesulfonyloxypropyl)-3-(2,3,4,6-tetra-O-pivaloyl-β-D-glucopyranosyloxy)-4-[2-(4-pivaloyloxyphenyl)ethyl]-1H-pyrazolo[3,4-b]pyridine (0.16 g) in N,N-dimethylformamide (3 mL) was added sodium azide (16 mg), and the mixture was stirred at100° C. for 1 hour. The reaction mixture was poured into water, and the resulting mixture was extracted with ethyl acetate. The extract was washed with water and brine, and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure, and the residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=3/1) to give 1-(3-azidopropyl)-3-(2,3,4,6-tetra-O-pivaloyl-β-D-glucopyranosyloxy)-4-[2-(4-pivaloyloxyphenyl)ethyl]-1H-pyrazolo[3,4-b]pyridine (94 mg). This material was dissolved in tetrahydrofuran (3 mL). To the solution was added 10% palladium-carbon powder (30 mg), and the mixture was stirred at room temperature under a hydrogen atmosphere for 3 hours. The insoluble material was removed by filtration, and the filtrate was concentrated under reduced pressure to give the title compound (90 mg).

Workup

  1. extractionthe resulting mixture was extracted with ethyl acetate
  2. washThe extract was washed with water and brine
  3. dry with materialdried over anhydrous sodium sulfate
  4. customThe solvent was removed under reduced pressure
  5. customthe residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=3/1)

Sources & evidence

ORD record
ord-0de85454ed2a4a6e8698e07bb0f81ec9
Source dataset
uspto-grants-2008_05
Patent number
US07375113B2

Reaction notes

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