Nitrogen → Cyclopentyl(2S,4E)-5-(4-bromophenyl)-2-[(tert-butoxycarbonyl)amino]pent-4-enoate

HRID 425025ノート

反応式

HRID 425025 の反応式
[C:1]([O:5][C:6]([NH:8][C@@H:9]([CH2:18][CH:19]=[CH2:20])[C:10]([O:12][CH:13]1[CH2:17][CH2:16][CH2:15][CH2:14]1)=[O:11])=[O:7])([CH3:4])([CH3:3])[CH3:2].[Br:21][C:22]1[CH:27]=[CH:26][C:25](I)=[CH:24][CH:23]=1.C([O-])(O)=O.[Na+].N#N>CCCC[N+](CCCC)(CCCC)CCCC.[I-].C(#N)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[Br:21][C:22]1[CH:27]=[CH:26][C:25](/[CH:20]=[CH:19]/[CH2:18][C@H:9]([NH:8][C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:7])[C:10]([O:12][CH:13]2[CH2:14][CH2:15][CH2:16][CH2:17]2)=[O:11])=[CH:24][CH:23]=1

参加物

8

反応物 4

HCID 947NitrogenHCID 115221-Bromo-4-iodobenzeneHCID 516892Sodium Bicarbonate2 回HCID 58150165cyclopentyl(2S)-2-[(tert-butoxycarbonyl)amino]pent-4-enoate

生成物 1

HCID 59243607Cyclopentyl(2S,4E)-5-(4-bromophenyl)-2-[(tert-butoxycarbonyl)amino]pent-4-enoate収率 52.5%

試薬・触媒・溶媒 3

HCID 67553Tetrabutylammonium Iodide触媒2 回HCID 167845palladium(II) acetate触媒2 回HCID 6342Acetonitrile溶媒

反応条件

温度
70 °C

実験手順

A solution of cyclopentyl(2S)-2-[(tert-butoxycarbonyl)amino]pent-4-enoate (0.88 g, 3.11 mmol), 1-bromo-4-iodobenzene (0.966 g, 3.42 mmol), TBAI (1.262 g, 3.42 mmol) and NaHCO3 (0.783 g, 9.32 mmol) in acetonitrile (10 ml) was purged with N2 and palladium acetate (0.070 g, 0.311 mmol) was added. The reaction was then heated at 70° C. overnight. LCMS showed incomplete conversion and so the reaction was purged with nitrogen again and a further 0.05 eq (35 mg) of Pd(OAc)2, 0.25 eq (460 mg) of TBAI and 0.25 eq of NaHCO3 (65 mg) was added and stirred for another 24 hr at 70° C. After cooling to room temperature, the solvent was removed under reduced pressure. The crude residue was absorbed onto silica and purified by column chromatography eluting with 10% EtOAc in iso-hexane. Yield=715 mg, 1.631 mmol, 52.5% yield. LCMS purity>90%: m/z 438 and 440 [M+H]+.

後処理

  1. additionwas added
  2. customso the reaction was purged with nitrogen again
  3. temperatureAfter cooling to room temperature
  4. customthe solvent was removed under reduced pressure
  5. customThe crude residue was absorbed onto silica
  6. custompurified by column chromatography
  7. washeluting with 10% EtOAc in iso-hexane

出典と根拠

ORDレコード
ord-9caaac9b2194498aa51c88deafa4e58e
出典データセット
uspto-grants-2012_01
特許番号
US08106091B2

反応ノート

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