tert-Butanol → HCID 10838503, compound

HRID 659838Notes

Reaction equation

HRID 659838 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 21672597HCID 21672597, compoundHCID 23667635Sodium periodate

Product 1

HCID 10838503HCID 10838503, compound

Reagents, catalysts & solvents 3

HCID 30318Osmium TetroxideCatalystHCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of nucleoside 2 (1.00 g, 2.09 mmol) in THF (5.4 cm3) and water (5.4 cm3) was added sodium periodate (1.34 g, 6.27 mmol) and a 2.5% solution of osmium tetraoxide in tert-butanol (w/w, 0.265 cm3, 19 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 (5.4 cm3) and water (5.4 cm3). The mixture was stirred at room temperature and sodium boronhydride (79 mg, 2.08 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 nucleoside 9 as a white solid material (488 mg, 48%). δH (CDCl3) 9.14 (1H, br s, NH), 7.60 (1H, d, J 1.1, 6-H), 7.40-7.22 (10H, m, Bn), 6.25 (1H, d, J 7.7, 1′-H), 4.59 (1H, d, J 7.1 Bn), 4.49 (1H, d, J 7.1 Bn), 4.39-3.30 (m, 8H, 4′-H, 2′-H, Bn, 5′-Ha, 5′-Hb, 2″-Ha, 2″-Hb), 2.23-2.00 (2H, m, 1″-Ha, 1″-Hb), 1.49 (3H, d, J 0.7, CH3). δC (CDCl3) 163.5 (C-4), 151.2 (C-2), 137.1, 136.5 (Bn), 135.7 (C-6), 128.7, 128.5, 128.2, 127.8, 127.6, 127.2 (Bn), 111.3 (C-5), 87.0, 82.7, 81.1, 78.3 (C-1′, C-2′, C-3′, C-4′), 73.7, 69.6 (Bn), 64.4 (C-5′), 57.0 (C-2″), 32.4 (C-1″), 11.8 (CH3) (Found. C, 63.9; H, 6.3; N, 5.4. C26H30N2O7, 0.25H2O requires C, 64.1; H, 6.3; N, 5.75%).

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 (5.4 cm3)
  6. stirringThe mixture was stirred at room temperature
  7. additionsodium boronhydride (79 mg, 2.08 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-f9c1c2b899c7459b856db8afdbbc4ce3
Source dataset
uspto-grants-2011_12
Patent number
US08080644B2

Reaction notes

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