Sodium Chlorate → methyl 2-[(3R,4R)-3-benzyloxycarbonylamino-2-oxo-4-(2-oxoethyl)azetidin-1-yl]-3-methylbut-2-enoate

HRID 1719341Notes

Reaction equation

HRID 1719341 reaction equation
[CH2:1]([O:8][C:9]([NH:11][C@@H:12]1[C@@H:15]([CH2:16][CH:17]=C)[N:14]([C:19](=[C:24]([CH3:26])[CH3:25])[C:20]([O:22][CH3:23])=[O:21])[C:13]1=[O:27])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Cl([O-])(=O)=[O:29].[Na+].I([O-])(=O)(=O)=O.[Na+]>O.O1CCCC1.[Cl-].[Na+].O.[Os](=O)(=O)(=O)=O>[CH2:1]([O:8][C:9]([NH:11][C@@H:12]1[C@@H:15]([CH2:16][CH:17]=[O:29])[N:14]([C:19](=[C:24]([CH3:26])[CH3:25])[C:20]([O:22][CH3:23])=[O:21])[C:13]1=[O:27])=[O:10])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

8

Reactant 3

HCID 516902Sodium ChlorateHCID 14581226methyl [(3R,4R)-3-benzyloxycarbonylamino-4-allyl-2-oxoazetidin-1-yl]-3-methylbut-2-enoateHCID 23667635Sodium periodate

Product 1

HCID 54489122methyl 2-[(3R,4R)-3-benzyloxycarbonylamino-2-oxo-4-(2-oxoethyl)azetidin-1-yl]-3-methylbut-2-enoateYield 84%

Reagents, catalysts & solvents 4

HCID 30318Osmium TetroxideCatalystHCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

A solution of osmium tetroxide (0.61 mg) in water (0.05 ml) was added to a solution of methyl 2-[(3R,4R)-3-benzyloxycarbonylamino-2-oxo-4-(prop-2-enyl)azetidin-1-yl]-3-methylbut-2-enoate (58 mg) and sodium chlorate (50 mg) in a mixture of tetrahydrofuran (1 ml) and water (1 ml) and the mixture was stirred for 17 hours at ambient temperature. Sodium periodate (60 mg) was then added and stirring was continued for 30 minutes. The resulting mixture was diluted with brine and extracted with ethyl acetate. The extract was washed successively with brine, brine containing sodium bicarbonate, and brine. The mixture was dried over magnesium sulfate and concentrated under reduced pressure to give an oil, which was chromatographed on silica gel (1.5 g, eluting with 2.5% methanol in dichloromethane) to give 49 mg of methyl 2-[(3R,4R)-3-benzyloxycarbonylamino-2-oxo-4-(2-oxoethyl)azetidin-1-yl]-3-methylbut-2-enoate.

Workup

  1. stirringstirring
  2. waitwas continued for 30 minutes
  3. extractionextracted with ethyl acetate
  4. washThe extract was washed successively with brine, brine
  5. additioncontaining sodium bicarbonate, and brine
  6. dry with materialThe mixture was dried over magnesium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customto give an oil, which
  9. customwas chromatographed on silica gel (1.5 g, eluting with 2.5% methanol in dichloromethane)

Sources & evidence

ORD record
ord-0498bb671e724dfe92ffb333a6a85e33
Source dataset
uspto-grants-1985_09
Patent number
US04539152

Reaction notes

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