Imidazole → 3,4,6-Tri-O-acetyl-2-azido-1-O-[tert-butyl(dimethyl)silyl]-2-deoxy-beta-D-glucopyranose

HRID 1761264Notes

Reaction equation

HRID 1761264 reaction equation
C([O:4][CH:5]1[O:18][C@H:17]([CH2:19][O:20][C:21](=[O:23])[CH3:22])[C@@H:12]([O:13][C:14](=[O:16])[CH3:15])[C@H:7]([O:8][C:9](=[O:11])[CH3:10])[C@H:6]1[N:24]=[N+:25]=[N-:26])(=O)C.C1(C)C=CC=CC=1.N1C=CN=C1.[Si:39](Cl)([C:42]([CH3:45])([CH3:44])[CH3:43])([CH3:41])[CH3:40]>C1COCC1.CO.C(Cl)Cl.CCOC(C)=O>[C:9]([O:8][C@H:7]1[C@H:12]([O:13][C:14](=[O:16])[CH3:15])[C@@H:17]([CH2:19][O:20][C:21](=[O:23])[CH3:22])[O:18][C@@H:5]([O:4][Si:39]([C:42]([CH3:45])([CH3:44])[CH3:43])([CH3:41])[CH3:40])[C@@H:6]1[N:24]=[N+:25]=[N-:26])(=[O:11])[CH3:10]

Participants

9

Reactant 4

HCID 795ImidazoleHCID 1140Toluene2×HCID 28928tert-Butyldimethylsilyl chlorideHCID 10872412HCID 10872412, compound

Product 1

HCID 162137033,4,6-Tri-O-acetyl-2-azido-1-O-[tert-butyl(dimethyl)silyl]-2-deoxy-beta-D-glucopyranoseYield 84%

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

1,3,4,6-Tetra-O-acetyl-2-azido-2-deoxy-D-glucopyranose (30.2 g, 80 mmol) was coevaporated twice with toluene and dissolved in THF and methanol (7:3, 300 mL). The solution was cooled to 0° C. and gaseous anhydrous ammonia was bubbled through at a modest rate. After 15 min, nitrogen was bubbled through the solution to remove excess ammonia and the solvent was removed in vacuo to afford a brown oil. The residue was coevaporated twice with toluene and dissolved in CH2Cl2 (150 mL). Imidazole (10.9 g, 160 mmol) and tert-butyldimethylsilyl chloride (13.3 g, 88 mmol) were added. After 2 h, the mixture was diluted with EtOAc, washed with water, 1 N HCl (2×) and water. The organic layer was dried over MgSO4, filtered, and the solvent was removed in vacuo. Crystallization from ethanol afforded 2 (29.8 g, 67 mmol, 84%) as colorless crystals. 1H-NMR (300 MHz, CDCl3) δ 5.00-4.90 (m, 2H), 4.63 (d, J=7.6 Hz, 1H), 4.20 (dd, J=5.9, 12.1 Hz, 1H), 4.09 (dd, J=2.6, 12.1 Hz, 1H), 3.70-3.64 (m, 1H), 3.48-3.40 (m, 1H), 2.10 (s, 3H), 2.08 (s, 3H), 2.00 (s, 3H), 0.95 (s, 9H), 0.15 (s, 6H). The spectral data was in agreement with the reported data. (W. Kinzy, R. R. Schmidt, Liebigs Ann. Chem. 1985, 1537-1545; for the procedure see: B. La Ferla, L. Lay, M. Guerrini, L. Poletti, L. Panza, G. Russo, Tetrahedron 1999, 55, 9867-9880).

Workup

  1. customgaseous anhydrous ammonia was bubbled through at a modest rate
  2. customnitrogen was bubbled through the solution
  3. customto remove excess ammonia
  4. customthe solvent was removed in vacuo
  5. customto afford a brown oil
  6. waitAfter 2 h
  7. washwashed with water, 1 N HCl (2×) and water
  8. dry with materialThe organic layer was dried over MgSO4
  9. filtrationfiltered
  10. customthe solvent was removed in vacuo
  11. customCrystallization from ethanol

Sources & evidence

ORD record
ord-86d85b32ddc34fd59b178aa76dffe623
Source dataset
uspto-grants-2005_01
Patent number
US06846917B2

Reaction notes

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