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

HRID 58831노트

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HRID 58831 반응식
[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]

참가 물질

9

반응물 4

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

생성물 1

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

시약·촉매·용매 4

HCID 23994Zinc촉매HCID 9811564Bis(dibenzylideneacetone)palladium촉매HCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenyl촉매HCID 6228Dimethylformamide용매3회

실험 절차

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.

후처리

  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)

출처 및 근거

ORD 기록
ord-0e0dea0f11534af2b8d415d69246786e
출처 데이터셋
uspto-grants-2016_09
특허 번호
US09434761B2

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