반응 #73896

ord-d85dd61b73594668aa72ea70f19db9a1

반응 조건

상세 조건
See reaction.notes.procedure_details.

후처리

  1. 1
    건조above was dried over P4O10 in vacuo for five hours
  2. 2
    기타to give 0.724 g drier material
  3. 3
    기타the mixture was sonicated for ca. 1 min
  4. 4
    기타to give a gelatinous mass
  5. 5
    기타to give a clear solution
  6. 6
    기타The solvents were removed under reduced pressure
  7. 7
    기타the mixture was partitioned between dichloromethane and 0.1M hydrochloric acid
  8. 8
    기타The organic phase was separated (hydrophobic frit)
  9. 9
    기타evaporated under reduced pressure
  10. 10
    기타The crude product was purified by flash column chromatography (12 g Biotage™ silica cartridge eluted with (i) 1:1 ethyl acetate:cyclohexane (ii) ethyl acetate (iii) ethyl acetate:methanol 9:1)

실험 절차

The acid (2RS)-2-(2,4-difluorophenyl)-2-[(3R,6R)-3-(2,3-dihydro-1H-inden-2-yl)-6-isobutyl-2,5-dioxopiperazin-1-yl]-ethanoic acid (0.747 g) prepared as described above was dried over P4O10 in vacuo for five hours to give 0.724 g drier material; this was dissolved in anhydrous dichloromethane:acetonitrile (1:1 v/v, 6 ml) and treated with triethylamine (0.223 ml) and BOP—Cl (bis(2-oxo-3-oxazolidinyl)phosphinic chloride, dissolved in anhydrous dichloromethane:acetonitrile (1:1 v/v, 6 ml) and treated with triethylamine (0.223 ml) and BOP—Cl (bis(2-oxo-3-oxazolidinyl)phosphinic chloride, 0.450 g) and the mixture was sonicated for ca. 1 min to give a gelatinous mass. After 10 minutes at room temperature a solution of dimethylamine in tetrahydrofuran (10 ml of 2M solution) was added to give a clear solution; this was left for 16 hours at room temperature. The solvents were removed under reduced pressure and the mixture was partitioned between dichloromethane and 0.1M hydrochloric acid. The organic phase was separated (hydrophobic frit) and evaporated under reduced pressure. The crude product was purified by flash column chromatography (12 g Biotage™ silica cartridge eluted with (i) 1:1 ethyl acetate:cyclohexane (ii) ethyl acetate (iii) ethyl acetate:methanol 9:1) to give the (2R)-2-(2,4-difluorophenyl)-2-[(3R,6R)-3-(2,3-dihydro-1H-inden-2-yl)-6-isobutyl-2,5-dioxopiperazin-1-yl]-N,N-dimethylethanamide as a colourless solid 0.285 g.

출처

DOI: 10.6084/m9.figshare.5104873.v1특허: US08541579B2uspto-grants-2013_09