Reaction #487516

ord-daf2b49341f7443d894bc00cc574df0c

Reaction equation

CO[C@H]1O[C@H](CN=[N+]=[N-])[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O
methyl 2,3,4-tri-O-acetyl-6-azido-6-deoxy-α-D-glucopyranoside
CO[C@H]1O[C@H](CN=[N+]=[N-])[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O
Methyl 2,3,4-tri-O-acetyl-6-azido-6-deoxy-α-D-glucopyranoside
O=S(=O)(O)O
sulfuric acid
CC(=O)O
acetic acid
→
CC(=O)O[C@H]1O[C@H](CN=[N+]=[N-])[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O
IV
Yield 82.0%
CC(=O)O[C@H]1O[C@H](CN=[N+]=[N-])[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O
1,2,3,4-tetra-O-acetyl-6-azido-6-deoxy-α-D-glucopyranose
Yield 82.0%

Reactants

CO[C@H]1O[C@H](CN=[N+]=[N-])[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O
methyl 2,3,4-tri-O-acetyl-6-azido-6-deoxy-α-D-glucopyranoside
CO[C@H]1O[C@H](CN=[N+]=[N-])[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O
Methyl 2,3,4-tri-O-acetyl-6-azido-6-deoxy-α-D-glucopyranoside
O=S(=O)(O)O
sulfuric acid
CC(=O)O
acetic acid
—
ice

Reagents

None

Solvents

CC(=O)OC(C)=O
acetic anhydride

Conditions

Detailed conditions
See reaction.notes.procedure_details.

Workup

  1. 1
    ExtractionExtraction with dichloromethane (3×50 mL)
  2. 2
    Washwashed with water, saturated sodium bicarbonate, brine
  3. 3
    Dryingdried over sodium sulfate
  4. 4
    Concentrationconcentrated
  5. 5
    OtherThe residue was purified by silica gel chromatography
  6. 6
    Washeluting with 1:1 hexane-ethyl acetate

Procedure

To a solution of methyl 2,3,4-tri-O-acetyl-6-azido-6-deoxy-α-D-glucopyranoside (III, 1.0 g, 2.9 mmol) in acetic acid (20 mL) and acetic anhydride (20 mL) at 0° C. was added sulfuric acid (97%, 1 mL) and the mixture was stirred at rt for 20 hr and then poured into ice (100 g). Extraction with dichloromethane (3×50 mL) and washed with water, saturated sodium bicarbonate, brine, dried over sodium sulfate and concentrated. The residue was purified by silica gel chromatography, eluting with 1:1 hexane-ethyl acetate, to give IV (886 mg, 82%) as a white foam. 1H NMR (500.1 MHz) (CD3Cl) δ: 6.28 (d, J=4.0 Hz, 1H), 5.41 (t, J=9.5 Hz, 1H), 5.03 (m, 2H), 4.03 (m, 1H), 3.24-3.37 (m, 2H), 2.13 (s, 3H), 2.04 (s, 3H), 1.99 (s, 3H), 1.95 (s, 3H). 13C NMR (125.8 MHz) (CDCl3) δ: 170.11, 169.53, 169.33, 168.62, 88.78, 70.83, 69.58, 69.08, 68.94, 50.61, 20.75, 20.55, 20.46, 20.34.

Source

DOI: 10.6084/m9.figshare.5104873.v1Patent: US08741567B2uspto-grants-2014_06