Iodine → (S)-Methyl 2-(tert-butoxycarbonylamino)-3-(3-oxocyclopent-1-enyl)propanoate

HRID 58831ノート

反応式

HRID 58831 の反応式
[C:1]([O:5][C:6]([NH:8][C@@H:9]([CH2:14]I)[C:10]([O:12][CH3:13])=[O:11])=[O:7])([CH3:4])([CH3:3])[CH3:2].II.I[C:19]1[CH2:23][CH2:22][C:21](=[O:24])[CH:20]=1.O>CN(C=O)C.[Zn].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.[Pd].[Pd].COC1C=CC=C(OC)C=1C1C=CC=CC=1P(C1CCCCC1)C1CCCCC1>[C:1]([O:5][C:6]([NH:8][C@@H:9]([CH2:14][C:19]1[CH2:23][CH2:22][C:21](=[O:24])[CH:20]=1)[C:10]([O:12][CH3:13])=[O:11])=[O:7])([CH3:4])([CH3:3])[CH3:2]

参加物

9

反応物 4

HCID 807IodineHCID 962WaterHCID 10903591methyl (2R)-2-(((tert-butoxy)carbonyl)amino)-3-iodopropanoateHCID 109766733-Iodo-2-cyclopenten-1-one

生成物 1

HCID 69933833(S)-Methyl 2-(tert-butoxycarbonylamino)-3-(3-oxocyclopent-1-enyl)propanoate収率 60%

試薬・触媒・溶媒 4

HCID 23994Zinc触媒HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenyl触媒HCID 6228Dimethylformamide溶媒3 回

実験手順

A solution of (R)-methyl 2-(tert-butoxycarbonylamino)-3-iodopropanoate (32.9 g, 0.100 mol) in DMF (20 mL) was added to a mixture of Zn (19.5 g, 0.300 mol) and iodine (6.6 g, 26 mmol) in DMF (30 mL) under nitrogen protection. The mixture was stirred for 1 h at ambient temperature. Then a solution of 3-iodocyclopent-2-enone (20.8 g, 0.100 mol) in DMF (50 mL), Pd2(dba)3 (2.3 g, 2.5 mmol) and S—Phos (2.1 g, 5.0 mmol) were added successively. The reaction mixture was stirred overnight at 50° C. The mixture was cooled to ambient temperature and water (100 mL) was added. The resulting mixture was extracted with EtOAc (150 mL×3). The combined organic extracts were dried over anhydrous sodium sulfate and concentrated. The residue was purified by flash column chromatography on silica gel (petroleum ether/EtOAc=5:1 to 2:1) to afford (S)-methyl 2-(tert-butoxycarbonylamino)-3-(3-oxocyclopent-1-enyl)propanoate (17 g, 60% yield) as a pale yellow oil.

後処理

  1. stirringThe reaction mixture was stirred overnight at 50° C
  2. temperatureThe mixture was cooled to ambient temperature
  3. extractionThe resulting mixture was extracted with EtOAc (150 mL×3)
  4. dry with materialThe combined organic extracts were dried over anhydrous sodium sulfate
  5. concentrationconcentrated
  6. customThe residue was purified by flash column chromatography on silica gel (petroleum ether/EtOAc=5:1 to 2:1)

出典と根拠

ORDレコード
ord-0e0dea0f11534af2b8d415d69246786e
出典データセット
uspto-grants-2016_09
特許番号
US09434761B2

反応ノート

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