Diisopropylamine → 4-Nitrobenzyl (5R,6S)-2-(cyclohepten-1-yl)-6-((1R)-1-hydroxyethyl)-1-carbapen-2-em-3-carboxylate

HRID 256779Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 256779
[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(NC(C)C)(C)C.FC(F)(F)C(OC(=O)C(F)(F)F)=O.COC1C=C(OC)C=C(OC)C=1P(C1C(OC)=CC(OC)=CC=1OC)C1C(OC)=CC(OC)=CC=1OC.[C:83]1([Sn](CCCC)(CCCC)CCCC)[CH2:89][CH2:88][CH2:87][CH2:86][CH2:85][CH:84]=1>C1COCC1.CN1CCCC1=O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C(Cl)(Cl)Cl.[Pd].[Pd]>[C:83]1([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])[CH2:89][CH2:88][CH2:87][CH2:86][CH2:85][CH:84]=1

Komponenten

9

Edukt 5

HCID 7912DiisopropylamineHCID 9845Trifluoroacetic anhydrideHCID 522987Tris(2,4,6-trimethoxyphenyl)phosphineHCID 10154755p-nitrobenzyl (3R,5R,6S)-6[(R)-1-hydroxyethyl]-2-oxocarbapenam-3-carboxylateHCID 19785831Cyclohepten-1-yl(tri-n-butyl)tin

Produkt 1

HCID 572988764-Nitrobenzyl (5R,6S)-2-(cyclohepten-1-yl)-6-((1R)-1-hydroxyethyl)-1-carbapen-2-em-3-carboxylateAusbeute 34,7 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 11029508Palladium, tris[mu-[(1,2-eta:4,5-eta)-(1E,4E)-1,5-diphenyl-1,4-pentadien-3-one]]di-, compd. with trichloromethane (1:1)KatalysatorHCID 8028TetrahydrofuranLösungsmittelHCID 13387N-methyl-2-pyrrolidoneLösungsmittel3×

Versuchsvorschrift

Under a nitrogen atmosphere, to a solution of 348 mg (1 mmol) of 4-nitrobenzyl (3R,5R,6S)-6-((1R)-1-hydroxyethyl) -2-oxo-1-carbapenam-3-carboxylate in THF (5 ml) was added 0.154 ml (1.1 mmol) of diisopropylamine at -78° C., and the mixture was stirred for 10 minutes. To the mixture was added 0.189 ml (1.08 mmol) of trifluoroacetic anhydride at the same temperature. After 15 minutes, to the mixture was added 5 ml of N-methylpyrrolidinone followed by 20.7 mg of tris(dibenzylideneacetone)dipalladium-chloroform, 42.5 mg (0.08 mmol) of tris(2,4,6-trimethoxyphenyl)phosphine, a solution of 389 mg (1.01 mmol) of cyclohepten-1-yl(tri-n-butyl)tin in N-methylpyrrolidinone (1 ml) and a solution of 225 mg (1.66 mmol) of N-methylpyrrolidinone (2 ml). The -78° C. bath was removed and the reaction mixture quickly raised to ambient temperature using a lukewarm water bath, and the mixture was stirred overnight at room temperature. The reaction mixture was poured into ethyl ether 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 148 mg (yield: 34.7%) of the title compound.

Aufarbeitung

  1. waitAfter 15 minutes
  2. customThe -78° C. bath was removed
  3. stirringthe mixture was stirred overnight at room temperature
  4. additionThe reaction mixture was poured into ethyl ether
  5. washthe organic layer was washed with water
  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 ethyl acetatehexane system)

Quellen und Nachweise

ORD-Eintrag
ord-4a2ed20146004e90bbbddd0b321fbdd4
Quelldatensatz
uspto-grants-1993_11
Patentnummer
US05258509

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