tert-Butanol → HCID 21672599, compound

HRID 434259Notes

Reaction equation

HRID 434259 reaction equation
[CH2:1]([C@@:4]1([O:28][CH2:29][C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[C@@H:8]([CH2:9][O:10][CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[O:7][C@@H:6]([N:18]2[CH:26]=[C:24]([CH3:25])[C:22](=[O:23])[NH:21][C:19]2=[O:20])[C@H:5]1[OH:27])[CH:2]=C.I([O-])(=O)(=O)=[O:37].[Na+].C(O)(C)(C)C>C1COCC1.O.[Os](=O)(=O)(=O)=O>[CH2:29]([O:28][C@:4]1([CH2:1][CH2:2][OH:37])[C@@H:8]([CH2:9][O:10][CH2:11][C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)[O:7][C@@H:6]([N:18]2[CH:26]=[C:24]([CH3:25])[C:22](=[O:23])[NH:21][C:19]2=[O:20])[C@H:5]1[OH:27])[C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1

Participants

7

Reactant 3

HCID 6386tert-ButanolHCID 21672598HCID 21672598, compoundHCID 23667635Sodium periodate

Product 1

HCID 21672599HCID 21672599, compound

Reagents, catalysts & solvents 3

HCID 30318Osmium TetroxideCatalystHCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of nucleoside 4 (2.26 g, 4.68 mmol) in THF (12 cm3) and water (12 cm3) was added sodium periodate (3.04 g, 14.2 mmol) and a 2.5% solution of osmium tetraoxide in tert-butanol (w/w, 0.603 cm3, 40 μmol). The solution was stirred at room temperature for 45 min. Water (25 cm3) was added and the solution was extracted with dichloromethane (2×50 cm3). The organic phase was washed with a saturated aqueous solution of sodium hydrogencarbonate (3×30 cm3) and dried (Na2SO4). The solvent was removed under reduced pressure and the residue was redissolved in THF (12 cm3) and water (12 cm3). The mixture was stirred at room temperature and sodium boronhydride (182 mg, 4.71 mmol) was added. After stirring for 1.5 h, water (25 cm3) was added and the solution was extracted with dichloromethane (2×50 cm3). The organic phase was washed with a saturated aqueous solution of sodium hydrogencarbonate (3×30 cm3) and dried (Na2SO4). The solvent was removed under reduced pressure and the residue was purified by silica gel column chromatography using dichloromethane/methanol (98:2, v/v) as eluent to give 5 as a white solid material (1.13 g, 49%). δH (CDCl3) 9.29 (1H, br s, NH), 7.47 (1H, d, J 1.1, 6-H), 7.38-7.25 (10 H, m, Bn), 6.22 (1H, d, J 3.4, 1′-H), 4.62 (2 H, s, Bn), 4.60 (1H, m, 4′-H), 4.46 (2 H, s, Bn), 4.35 (1H, dd, J 3.4, 7.5, 2′-H), 3.83-3.73 (4 H, m, 2×5′-H, 2×2″-H), 2.67 (1 H, br s, OH), 2.07-2.01 (2 H, m, 2×1″-H), 1.77 (3 H, d, J 0.5, CH3). δC (CDCl3) 164.3 (C-4), 150.3 (C-2), 137.6, 137.4 (Bn, C-6), 136.7 (Bn), 128.6, 128.4, 128.2, 127.8, 127.6, 127.3, 127.1 (Bn), 108.4 (C-S), 88.0, 87.7, 81.6, 74.7 (C-1′, C-2′, C-3′, C-4′), 73.7, 69.6 (Bn), 64.6 (C-5′), 57.7 (C-2″), 28.6 (C-1″), 12.4 (CH3). FAB-MS m/z 483 [M+H]+, 505 [M+Na]+ (Found: C, 63.6; H, 6.2; N, 5.4. C26 H30N2O7,0.5 H2O requires C, 63.5; H 6.4; N, 5.7%).

Workup

  1. extractionthe solution was extracted with dichloromethane (2×50 cm3)
  2. washThe organic phase was washed with a saturated aqueous solution of sodium hydrogencarbonate (3×30 cm3)
  3. dry with materialdried (Na2SO4)
  4. customThe solvent was removed under reduced pressure
  5. dissolutionthe residue was redissolved in THF (12 cm3)
  6. stirringThe mixture was stirred at room temperature
  7. additionsodium boronhydride (182 mg, 4.71 mmol) was added
  8. stirringAfter stirring for 1.5 h
  9. additionwater (25 cm3) was added
  10. extractionthe solution was extracted with dichloromethane (2×50 cm3)
  11. washThe organic phase was washed with a saturated aqueous solution of sodium hydrogencarbonate (3×30 cm3)
  12. dry with materialdried (Na2SO4)
  13. customThe solvent was removed under reduced pressure
  14. customthe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-136f8edef2664f839fb922fd64b2ae59
Source dataset
uspto-grants-2003_12
Patent number
US06670461B1

Reaction notes

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