Phosphate → HCID 131719087, compound

HRID 849307Notes

Reaction equation

HRID 849307 reaction equation
C([O:4][C:5]([CH2:7][N:8]1[C@H:11]([C@@H:12]([CH3:31])[C:13](N2C3(CCCCC3)OC3C=CC=CC=3C2=O)=[O:14])[C@@H:10]([C@H:32]([O:34][Si:35]([C:38]([CH3:41])([CH3:40])[CH3:39])([CH3:37])[CH3:36])[CH3:33])[C:9]1=[O:42])=[O:6])C=C.C[Si]([N-][Si](C)(C)C)(C)C.[Na+].C[Si](Cl)(C)C.[C:58]1([P:64](Cl)([C:66]2[CH:71]=[CH:70][CH:69]=[CH:68][CH:67]=2)=[O:65])[CH:63]=[CH:62][CH:61]=[CH:60][CH:59]=1.P([O-])([O-])([O-])=O>O1CCCC1>[Si:35]([O:34][C@@H:32]([C@H:10]1[C:9](=[O:42])[N:8]2[C:7]([C:5]([OH:4])=[O:6])=[C:13]([O:14][P:64]([C:66]3[CH:67]=[CH:68][CH:69]=[CH:70][CH:71]=3)([C:58]3[CH:63]=[CH:62][CH:61]=[CH:60][CH:59]=3)=[O:65])[C@H:12]([CH3:31])[C@H:11]12)[CH3:33])([C:38]([CH3:40])([CH3:41])[CH3:39])([CH3:36])[CH3:37]

Participants

7

Reactant 5

HCID 1061PhosphateHCID 6397ChlorotrimethylsilaneHCID 73910Diphenylphosphinic chlorideHCID 2724254Sodium bis(trimethylsilyl)amideHCID 10326224HCID 10326224, compound

Product 1

HCID 131719087HCID 131719087, compoundYield 95.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-50 °C

Procedure

A solution of 1.2 g of 3-{(2R)-2-[(3S,4R)-1-allyloxycarbonylmethyl-3-[(1R)-1-t-butyldimethylsilyloxyethyl]-2-oxoazetidin-4-yl]propionyl}-spiro[2,3-dihydro-4H-1,3-benzoxazine-2,1'-cyclohexan]-4-one in 6 ml of tetrahydrofuran is added dropwise to 4.4 ml of 1 M sodium bis(trimethylsilyl)amide solution (solvent: tetrahydrofuran) at a temperature from -20° C. to -30° C. during one minute. 261 mg of trimethylsilyl chloride are added thereto at -50° C. and the mixture is stirred for 2 minutes. Then, 645 mg of diphenylphosphoryl chloride are added thereto at -50° C. and the mixture is stirred for 2 hours at 0° C. The reaction mixture is poured into 50 ml of 0.2 M phosphate buffer (pH 7.0) and the mixture is extracted with ethyl acetate. The extract is washed, dried and evaporated to remove the solvent. Isopropyl ether is added to the residue and the resulting precipitates of 355 mg of spiro[2,3-dihydro-4H-1,3-benzoxazine-2,1'-cyclohexan]-4-one are removed by filtration. The filtrate is condensed to obtain 1.04 g of (1R,5R,6S)-6-[(1R)-1-t-butyldimethylsilyloxyethyl]-1-methyl-2-diphenylphosphoryloxy-carbapen-2-em-3-carboxylic acid.allyl ester as syrup.

Workup

  1. stirringat -50° C. and the mixture is stirred for 2 hours at 0° C
  2. extractionthe mixture is extracted with ethyl acetate
  3. washThe extract is washed
  4. customdried
  5. customevaporated
  6. customto remove the solvent
  7. additionIsopropyl ether is added to the residue
  8. customthe resulting precipitates of 355 mg of spiro[2,3-dihydro-4H-1,3-benzoxazine-2,1'-cyclohexan]-4-one
  9. customare removed by filtration
  10. customcondensed

Sources & evidence

ORD record
ord-78c4779b9ac34e8c9ccb92e2454bc127
Source dataset
uspto-grants-2000_01
Patent number
US06011150

Reaction notes

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