1,4-Cyclohexadiene → HCID 57313078, compound

HRID 434278Notes

Reaction equation

HRID 434278 reaction equation
C([O:8][C@H:9]1[C@H:13]2[O:14][CH2:15][C@:10]1([CH2:32][O:33]CC1C=CC=CC=1)[O:11][C@H:12]2[N:16]1[CH:31]=[CH:30][C:20]([NH:21]C(=O)C2C=CC=CC=2)=[N:19][C:17]1=[O:18])C1C=CC=CC=1.C1CC=CCC=1>CO.[Pd]>[OH:8][C@H:9]1[C@H:13]2[O:14][CH2:15][C@:10]1([CH2:32][OH:33])[O:11][C@H:12]2[N:16]1[CH:31]=[CH:30][C:20]([NH2:21])=[N:19][C:17]1=[O:18]

Participants

5

Reactant 2

HCID 123431,4-Cyclohexadiene2×HCID 20610789HCID 20610789, compound

Product 1

HCID 57313078HCID 57313078, compound

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalyst2×HCID 887MethanolSolvent

Procedure

To a solution of nucleoside 57 (0.3 g, 0.55 mmol) in anhydrous methanol (22 cm3) were added 1,4-cyclohexadiene (5.0 cm3) and 10% palladium on carbon (0.314 g). The mixture was stirred under reflux for 18 h. Additional 10% palladium on carbon (0.380 g) and 1,4-cyclohexadiene (5.5 cm3) were added and the mixture was refluxed for 54 h. The reaction mixture was filtered through a pad of silica gel which was subsequently washed with methanol (1 500 cm3). The combined filtrate was evaporated under reduced pressure and the residue was purified by silica gel column chromatography using dichloromethane/methanol (92.5:7.5, v/v) as eluent to give compound 57A as a white solid material (0.051 g, 36%). δH ((CD3)2SO) 7.73 (1H, d, J 7.7, 6-H), 7.12-7.20 (2H, br s, NH2), 5.74 (1H, d, J 7.7, 5-H), 5.61 (1H, br s, 3′-OH), 5.39 (1H, s, 1′-H), 5.12 (1H, m, 5′-OH), 4.08 (1H, s, 2′-H), 3.80 (1H, d, J 7.7, 1″-H), 3.81 (1H, s, 3′-H), 3.74 (2H, m, 5′-Ha, 5′-Hb), 3.63 (1H, d, J 7.7, 1″-Hb). δC ((CD3)2SO) 165.66 (C-4), 154.58 (C-2), 139.68 (C-6), 93.19 (C-5), 88.42, 86.73 (C-1′, C-4′), 78.87, 70.85, 68.32, 56.04 (C-2′, C-1″, C-3′, C-5′). FAB-MS m/z 256 [M+H]+.

Workup

  1. temperatureunder reflux for 18 h
  2. temperaturethe mixture was refluxed for 54 h
  3. filtrationThe reaction mixture was filtered through a pad of silica gel which
  4. washwas subsequently washed with methanol (1 500 cm3)
  5. customThe combined filtrate was evaporated under reduced pressure
  6. customthe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-14a65fe2df37453f8ad336990f653953
Source dataset
uspto-grants-2003_12
Patent number
US06670461B1

Reaction notes

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