Bromobenzene → Methyl 5-oxo-1-phenylprolinate

HRID 554113

반응식

HRID 554113 반응식
[CH2:1]([O:3][C:4](=[O:11])[C@H:5]1[CH2:9][CH2:8][C:7](=[O:10])[NH:6]1)C.Br[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.C(=O)([O-])[O-].[Cs+].[Cs+].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>O1CCOCC1.CO.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]>[O:10]=[C:7]1[N:6]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[C@H:5]([C:4]([O:3][CH3:1])=[O:11])[CH2:9][CH2:8]1

참가 물질

8

반응물 4

HCID 7961BromobenzeneHCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 643508ethyl (2R)-5-oxopyrrolidine-2-carboxylate

생성물 1

HCID 42260998Methyl 5-oxo-1-phenylprolinate수율 28%

시약·촉매·용매 3

HCID 9811564Bis(dibenzylideneacetone)palladium촉매HCID 887Methanol용매HCID 312751,4-Dioxane용매

실험 절차

D-pyroglutamic acid ethyl ester (0.200 g, 1.27 mmol) was dissolved in dioxane (5 ml) and treated with tris(dibenzylideneacetone)dipalladium (0) (0.058 g, 0.06 mmol), bromobenzene (0.351 ml, 1.53 mmol), cesium carbonate (0.621 g, 1.91 mmol) and Xantphos™ (0.110 g, 0.19 mmol). The resulting mixture was heated at reflux overnight and then allowed to cool to room temperature. The mixture was diluted with methanol and filtered. The filtrate was evaporated in vacuo and then partitioned between dichloromethane and saturated aqueous sodium hydrogen carbonate. The aqueous layer was extracted with more dichloromethane (3 aliquots) and then the combined organic layers were washed with brine and dried over magnesium sulphate. Evaporation of the solvent gave a bright yellow residue which was purified by flash silica column chromatography, eluting with a gradient of 0-50% ethyl acetate in hexane, to give methyl 5-oxo-1-phenylprolinate (0.078 g) as a yellow oil. This was used in the next step without further purification.

후처리

  1. temperatureThe resulting mixture was heated
  2. temperatureat reflux overnight
  3. filtrationfiltered
  4. customThe filtrate was evaporated in vacuo
  5. custompartitioned between dichloromethane and saturated aqueous sodium hydrogen carbonate
  6. extractionThe aqueous layer was extracted with more dichloromethane (3 aliquots)
  7. washthe combined organic layers were washed with brine
  8. dry with materialdried over magnesium sulphate
  9. customEvaporation of the solvent
  10. customgave a bright yellow residue which
  11. customwas purified by flash silica column chromatography
  12. washeluting with a gradient of 0-50% ethyl acetate in hexane

출처 및 근거

ORD 기록
ord-3f7379b7d5b645a99c8266489442eda3
출처 데이터셋
uspto-grants-2011_11
특허 번호
US08048907B2

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