Triethylamine → (2R,3R,4R,5R,6R)-5-acetamido-2-(acetoxymethyl)-6-(2-(2-(2-azidoethoxy)ethoxy)ethoxy)-tetrahydro-2H-pyran-3,4-diyl diacetate

HRID 526274Notes

Reaction equation

HRID 526274 reaction equation
[C:1]([O:4][C@H:5]1[C@@H:13]([CH2:14][O:15][C:16](=[O:18])[CH3:17])[O:12][C@H:11]2[C@H:7]([N:8]=[C:9]([CH3:19])[O:10]2)[C@H:6]1[O:20][C:21](=[O:23])[CH3:22])(=[O:3])[CH3:2].[N:24]([CH2:27][CH2:28][O:29][CH2:30][CH2:31][O:32][CH2:33][CH2:34][OH:35])=[N+:25]=[N-:26].CC1(C)C2(CS(O)(=O)=O)C(CC1CC2)=O.CCN(CC)CC>C(Cl)Cl>[C:1]([O:4][C@@H:5]1[C@H:6]([O:20][C:21](=[O:23])[CH3:22])[C@@H:7]([NH:8][C:9](=[O:10])[CH3:19])[C@H:11]([O:35][CH2:34][CH2:33][O:32][CH2:31][CH2:30][O:29][CH2:28][CH2:27][N:24]=[N+:25]=[N-:26])[O:12][C@@H:13]1[CH2:14][O:15][C:16](=[O:18])[CH3:17])(=[O:3])[CH3:2]

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 18462Bicyclo[2.2.1]heptane-1-methanesulfonic acid, 7,7-dimethyl-2-oxo-, (1S)-HCID 110084382-(2-(2-Azidoethoxy)ethoxy)ethanolHCID 11278902(3aR,5R,6R,7R,7aR)-5-(acetoxymethyl)-2-methyl-5,6,7,7a-tetrahydro-3aH-pyrano[3,2-d]oxazole-6,7-diyl diacetate

Product 1

HCID 11466235(2R,3R,4R,5R,6R)-5-acetamido-2-(acetoxymethyl)-6-(2-(2-(2-azidoethoxy)ethoxy)ethoxy)-tetrahydro-2H-pyran-3,4-diyl diacetate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

This protocol was modified to synthesis 5β exclusively. Briefly, compound 2 (1.0 g, 3.03 mmol) and alcohol 4 (1.60 g, 9.11 mmol) were dissolved in anhydrous DCM (20 mL), followed by addition of dried 4 A° MS (0.4 g) and reaction mixture stirred at room temperature for 20 minutes under N2. CSA (camphor sulphonic acid, 0.615 g, 9.0 mL, 9.1 mmol) was added at room temperature and 8 hours, followed by heating to 45° C. for 24 hours. The reaction mixture was cooled to room temperature, neutralized with Et3N (0.2 mL, pH 7.5), diluted with DCM (100 mL) and extracted using saturated NaHCO3 solution. The organic layer was washed with water, brine and dried over Na2SO4. Solvents were evaporated under reduced pressure and the residue purified by silica gel column chromatography using DCM:EtOAc:MeOH (8.0:1.5:0.5) to obtain compound 5β (1.15 g, 85%). The spectral data matched with above compound 5β.

Workup

  1. customThis protocol was modified to synthesis 5β exclusively
  2. additionfollowed by addition
  3. customof dried
  4. custom4 A° MS (0.4 g) and reaction mixture
  5. temperatureby heating to 45° C. for 24 hours
  6. temperatureThe reaction mixture was cooled to room temperature
  7. extractionextracted
  8. washThe organic layer was washed with water, brine
  9. dry with materialdried over Na2SO4
  10. customSolvents were evaporated under reduced pressure
  11. customthe residue purified by silica gel column chromatography
  12. customto obtain compound 5β (1.15 g, 85%)

Sources & evidence

ORD record
ord-8bc1cd029b594172b52ad039f3cbe316
Source dataset
uspto-grants-2016_05
Patent number
US09345781B2

Reaction notes

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