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

HRID 1948378ノート

反応式

HRID 1948378 の反応式
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]

参加物

5

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-78 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-43b8dc5865594f0ca391ca680599b5a5
出典データセット
uspto-grants-2013_03
特許番号
US08399489B2

反応ノート

読み込み中…