Trifluoromethanesulfonic anhydride → 4-Nitrobenzyl (5R,6S)-2-(4-dimethylaminocarbonylphenyl)-6-((1R)-1-hydroxyethyl)-1-carbapen-2-em-3-carboxylate

HRID 256780Notes

Reaction equation

HRID 256780 reaction equation
[OH:1][C@@H:2]([C@H:4]1[C:24](=[O:25])[N:6]2[C@@H:7]([C:11]([O:13][CH2:14][C:15]3[CH:20]=[CH:19][C:18]([N+:21]([O-:23])=[O:22])=[CH:17][CH:16]=3)=[O:12])[C:8](=O)[CH2:9][C@H:5]12)[CH3:3].C(N(C(C)C)CC)(C)C.FC(F)(F)S(OS(C(F)(F)F)(=O)=O)(=O)=O.[O-]S(C(F)(F)F)(=O)=O.O1C=CC=C1P(C1OC=CC=1)C1OC=CC=1.[CH3:74][N:75]([CH3:97])[C:76]([C:78]1[CH:83]=[CH:82][C:81]([Sn](CCCC)(CCCC)CCCC)=[CH:80][CH:79]=1)=[O:77]>C(#N)C.CN1CCCC1=O.[Cl-].[Zn+2].[Cl-].C(OCC)(=O)C>[CH3:74][N:75]([CH3:97])[C:76]([C:78]1[CH:83]=[CH:82][C:81]([C:8]2[CH2:9][C@@H:5]3[C@@H:4]([C@H:2]([OH:1])[CH3:3])[C:24](=[O:25])[N:6]3[C:7]=2[C:11]([O:13][CH2:14][C:15]2[CH:20]=[CH:19][C:18]([N+:21]([O-:23])=[O:22])=[CH:17][CH:16]=2)=[O:12])=[CH:80][CH:79]=1)=[O:77]

Participants

11

Reactant 6

HCID 67749Trifluoromethanesulfonic anhydrideHCID 81531DiisopropylethylamineHCID 521585Tris(furan-2-yl)phosphaneHCID 2758875TrifluoromethanesulfonateHCID 10154755p-nitrobenzyl (3R,5R,6S)-6[(R)-1-hydroxyethyl]-2-oxocarbapenam-3-carboxylateHCID 19785832(4-Dimethylaminocarbonylphenyl)tri-n-butyltin

Product 1

HCID 570274904-Nitrobenzyl (5R,6S)-2-(4-dimethylaminocarbonylphenyl)-6-((1R)-1-hydroxyethyl)-1-carbapen-2-em-3-carboxylate

Reagents, catalysts & solvents 4

HCID 3007855ZincchlorideCatalystHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent2×HCID 13387N-methyl-2-pyrrolidoneSolvent

Procedure

Under a nitrogen atmosphere, to a solution of 128 mg (0.368 mmol) of 4-nitrobenzyl (3R,5R,6S)-6-((1R)-1-hydroxyethyl) -2-oxo-1-carbapenam-3-carboxylate in acetonitrile (3 ml) was added 0.065 ml (0.37 mmol) of diisopropylethylamine followed by 0.062 ml (0.37 mmol) of trifluoromethanesulfonic anhydride at -45° C., and the mixture was stirred for 30 minutes. To the mixture was added ethyl acetate, and the organic layer was washed with saturated aqueous sodium bicarbonate followed by saturated aqueous sodium chloride. After the extract was dried over anhydrous magnesium sulfate, the solvent was removed. To the crude triflate was added 113 mg (0.83 mmol) of zinc chloride, 5.3 mg (0.0091 mmol) of bis(benzylideneacetone)palladium(0) and 4.4 mg (0.019 mmol) of tri(2-furyl)phosphine. Under a nitrogen atmosphere, to the mixture was added a solution of 191 mg (0.4436 mmol) of (4-dimethylaminocarbonylphenyl)tri-n-butyltin in N-methylpyrrolidinone (6 ml), and the mixture was stirred for 2 hours at room temperature. To the reaction mixture was added ethyl acetate, and the organic layer was washed with water (50 ml×2) followed by saturated aqueous sodium chloride. After the extract was dried over anhydrous magnesium sulfate, the solvent was removed. The residue was purified by silica gel column chromatography (elution with 3% methanol-chloroform) to give 9.lmg (yield: 27.9%) of the title compound.

Workup

  1. washthe organic layer was washed with saturated aqueous sodium bicarbonate
  2. dry with materialAfter the extract was dried over anhydrous magnesium sulfate
  3. customthe solvent was removed
  4. stirringthe mixture was stirred for 2 hours at room temperature
  5. washthe organic layer was washed with water (50 ml×2)
  6. dry with materialAfter the extract was dried over anhydrous magnesium sulfate
  7. customthe solvent was removed
  8. customThe residue was purified by silica gel column chromatography (elution with 3% methanol-chloroform)

Sources & evidence

ORD record
ord-b490d303be2b4e3888698e8461fe811e
Source dataset
uspto-grants-1993_11
Patent number
US05258509

Reaction notes

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