Water → HCID 86614391, compound

HRID 1673313Notes

Reaction equation

HRID 1673313 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

Conditions

Temperature
100 °C

Procedure

To a solution of 1-(3-hydroxypropyl)-3-(2,3,4,6-tetra-O-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 ethylacetate. 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 at 100° 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-d06411db95564b878c1e571a473ad2ce
Source dataset
uspto-grants-2011_08
Patent number
US07998975B2

Reaction notes

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