Tributylstannane → 6,7,8-Triacetoxy-1-methyl-3-oxo-2-oxa-4-azabicyclo[3.3.1]nonane

HRID 1982186Notes

Reaction equation

HRID 1982186 reaction equation
[C:1]([O:4][CH:5]1[CH:12]([O:13][C:14](=[O:16])[CH3:15])[CH:11]([O:17][C:18](=[O:20])[CH3:19])[C:10]2([CH2:22]Br)[CH2:21][CH:6]1[NH:7][C:8](=[O:24])[O:9]2)(=[O:3])[CH3:2].C([SnH](CCCC)CCCC)CCC.N(C(C)(C)C#N)=NC(C)(C)C#N>C1(C)C=CC=CC=1>[C:1]([O:4][CH:5]1[CH:12]([O:13][C:14](=[O:16])[CH3:15])[CH:11]([O:17][C:18](=[O:20])[CH3:19])[C:10]2([CH3:22])[CH2:21][CH:6]1[NH:7][C:8](=[O:24])[O:9]2)(=[O:3])[CH3:2]

Participants

5

Reactant 3

HCID 5948TributylstannaneHCID 6547AzobisisobutyronitrileHCID 13309815HCID 13309815, compound

Product 1

HCID 155868356,7,8-Triacetoxy-1-methyl-3-oxo-2-oxa-4-azabicyclo[3.3.1]nonane

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

6,7,8-Triacetoxy-1-bromomethyl-3-oxo-2-oxa-4-azabicyclo[3.3.1]nonane (as described in Example 1 of the Japanese Patent Application No. 144309/1981, pp. 37) (800 mg) is dissolved in toluene (50 ml), and tri-n-butyltin hydride (1 ml) and α,α'-azo-bis-isobutyronitrile (100 mg) are added to the solution, followed by reflux with stirring for 1 hour. The reaction mixture is concentrated under reduced pressure, and petroleum ether is added to the residue, which is allowed to stand overnight in a refrigerator. The resulting precipitates are recovered by filtration, dried and chromatographed on a column of silica gel (180 ml), followed by elution with ethyl acetate. The eluate is concentrated under reduced pressure, and ethyl ether-petroleum ether (1:1) is added to the residue, which is allowed to stand overnight in a refrigerator to produce crystalline 6,7,8-triacetoxy-1-methyl-3-oxo-2-oxa-4-azabicyclo[3.3.1]nonane (510 mg).

Workup

  1. temperatureby reflux
  2. concentrationThe reaction mixture is concentrated under reduced pressure, and petroleum ether
  3. additionis added to the residue, which
  4. waitto stand overnight in a refrigerator
  5. customThe resulting precipitates
  6. filtrationare recovered by filtration
  7. customdried
  8. customchromatographed on a column of silica gel (180 ml)
  9. washfollowed by elution with ethyl acetate
  10. concentrationThe eluate is concentrated under reduced pressure, and ethyl ether-petroleum ether (1:1)
  11. additionis added to the residue, which
  12. waitto stand overnight in a refrigerator

Sources & evidence

ORD record
ord-d9cd4ebabf5643a790194942cdc4595b
Source dataset
uspto-grants-1986_06
Patent number
US04595678

Reaction notes

Loading…