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

HRID 256778Notes

Reaction equation

HRID 256778 reaction equation
[OH:1][C@@H:2]([C@H:4]1[C:24](=[O:25])[N:6]2[CH: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].[CH:26](N(C(C)C)CC)(C)[CH3:27].FC(F)(F)S(OS(C(F)(F)F)(=O)=O)(=O)=O.O1C=CC=C1P(C1OC=CC=1)C1OC=CC=1.C([Sn](CCCC)(CCCC)CCCC)=C>C(#N)C.CN1CCCC1=O.[Cl-].[Zn+2].[Cl-].C(OCC)(=O)C>[OH:1][C@@H:2]([C@H:4]1[C:24](=[O:25])[N:6]2[C: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]([CH:26]=[CH2:27])[CH2:9][C@H:5]12)[CH3:3]

Participants

10

Reactant 5

HCID 67749Trifluoromethanesulfonic anhydrideHCID 81531DiisopropylethylamineHCID 81998TributylvinyltinHCID 521585Tris(furan-2-yl)phosphaneHCID 11198839(4-Nitrophenyl)methyl (5R,6S)-6-((1R)-1-hydroxyethyl)-3,7-dioxo-1-azabicyclo(3.2.0)heptane-2-carboxylate

Product 1

HCID 572183924-Nitrobenzyl (5R,6S)-6-((1R)-1-hydroxyethyl)-2-vinyl-1-carbapen-2-em-3-carboxylateYield 47.9%

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 (5R,6S)-6-((1R)-1-hydroxyethyl) -2-oxo-1-carbapenam-3-carboxylate in acetonitrile (3 ml), followed by 0.065 ml (0.37 mmol) of diisopropylethylamine at -45° C., followed by 0.062 ml (0.37 mmol) of trifluoromethanesulfonic anhydride, and the mixture was stirred for 2 hours at the same temperature. To the reaction mixture was added ethyl acetate (3 ml), 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. The residual triflate was used the next reaction without purification. To 181 mg of this crude product was added 108 mg (0.79 mmol) of zinc chloride, 5.1 mg (0.0087 mmol) of bis(benzylideneacetone)-palladium(0), and 4.2 mg (0.018 mmol) of tri(2-furyl)phosphine was added a solution of 132 mg (0.416 mmol) of vinyl(tri-n-butyl)tin 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 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 ethyl acetatehexane system) to give 60.3 mg (yield: 47.9%) 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. customthe next reaction
  5. customwithout purification
  6. stirringthe mixture was stirred for 2 hours at room temperature
  7. washthe organic layer was washed with water
  8. dry with materialAfter the extract was dried over anhydrous magnesium sulfate
  9. customthe solvent was removed
  10. customThe residue was purified by silica gel column chromatography (elution with ethyl acetatehexane system)

Sources & evidence

ORD record
ord-877551b1f58f4693bf6df20afb5b3a14
Source dataset
uspto-grants-1993_11
Patent number
US05258509

Reaction notes

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