N-Fluorobenzenesulfonimide → tert-butyl 4-chloro-3-fluoro-5-methyl-1-{[2-(trimethylsilyl)ethoxy]methyl}-1H-pyrrole-2-carboxylate

HRID 1948378Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1948378
Br[C:2]1[C:6]([Cl:7])=[C:5]([CH3:8])[N:4]([CH2:9][O:10][CH2:11][CH2:12][Si:13]([CH3:16])([CH3:15])[CH3:14])[C:3]=1[C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18].[Li]CCCC.C1C=CC(S(N(S(C2C=CC=CC=2)(=O)=O)[F:39])(=O)=O)=CC=1>C1COCC1>[Cl:7][C:6]1[C:2]([F:39])=[C:3]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[N:4]([CH2:9][O:10][CH2:11][CH2:12][Si:13]([CH3:16])([CH3:15])[CH3:14])[C:5]=1[CH3:8]

Komponenten

5

Edukt 3

HCID 588007N-FluorobenzenesulfonimideHCID 59406885tert-butyl 3-bromo-4-chloro-5-methyl-1-{[2-(trimethylsilyl)ethoxy]methyl}-1H-pyrrole-2-carboxylate2×HCID 178418339Butyllithium

Produkt 1

HCID 68516579tert-butyl 4-chloro-3-fluoro-5-methyl-1-{[2-(trimethylsilyl)ethoxy]methyl}-1H-pyrrole-2-carboxylate

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

tert-butyl 3-bromo-4-chloro-5-methyl-1-{[2-(trimethylsilyl)ethoxy]methyl}-1H-pyrrole-2-carboxylate (Intermediate 265, 480 mg, 1.13 mmol) was dissolved in dry THF (8 ml), cooled down to −78° C., n-BuLi (2.5M in Hexane, 3.39 mmol) was added dropwise into the mixture via syringe and the mixture was stirred at −78° C. for 30 min followed by a quick addition of N-Fluorobenzensulfonimide (1.25 g, 3.96 mmol in 5 ml of THF/Toluene 1:1), the resulting mixture was then stirred at −78° C. for 30 min and slowly warmed up to room temperature during a period of 12 hrs. The reaction was quenched at 0° C. with drops of saturated NH4Cl solution and further diluted with EtOAc (50 ml). The organic phase was washed with brine and dried over anhydrous MgSO4, concentrated to an oil and purified by flash column chromatography eluted with 10% EtOAc in Hexanses. The desired product was obtained as an oil (125 mg).

Aufarbeitung

  1. stirringthe resulting mixture was then stirred at −78° C. for 30 min
  2. temperatureslowly warmed up to room temperature during a period of 12 hrs
  3. customThe reaction was quenched at 0° C. with drops of saturated NH4Cl solution
  4. additionfurther diluted with EtOAc (50 ml)
  5. washThe organic phase was washed with brine
  6. dry with materialdried over anhydrous MgSO4
  7. concentrationconcentrated to an oil
  8. custompurified by flash column chromatography
  9. washeluted with 10% EtOAc in Hexanses

Quellen und Nachweise

ORD-Eintrag
ord-43b8dc5865594f0ca391ca680599b5a5
Quelldatensatz
uspto-grants-2013_03
Patentnummer
US08399489B2

Notizen zur Reaktion

Wird geladen…