Hexachloroethane → (S)-tert-butyl 2-(5-(4-bromophenyl)oxazol-2-yl)pyrrolidine-1-carboxylate

HRID 18355

반응식

HRID 18355 반응식
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=O)[CH2:9][NH:10][C:11]([C@@H:13]2[CH2:17][CH2:16][CH2:15][N:14]2[C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])=[O:12])=[CH:4][CH:3]=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C(N(C(C)C)CC)(C)C.ClC(Cl)(Cl)C(Cl)(Cl)Cl>CC#N.C(OCC)(=O)C>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2[O:12][C:11]([C@@H:13]3[CH2:17][CH2:16][CH2:15][N:14]3[C:18]([O:20][C:21]([CH3:24])([CH3:22])[CH3:23])=[O:19])=[N:10][CH:9]=2)=[CH:6][CH:7]=1

참가 물질

7

반응물 4

HCID 6214Hexachloroethane2회HCID 11776Triphenylphosphine2회HCID 81531DiisopropylethylamineHCID 56605334(S)-tert-butyl 2-((2-(4-bromophenyl)-2-oxoethyl)carbamoyl)pyrrolidine-1-carboxylate

생성물 1

HCID 59345150(S)-tert-butyl 2-(5-(4-bromophenyl)oxazol-2-yl)pyrrolidine-1-carboxylate수율 63.3%

시약·촉매·용매 2

HCID 6342Acetonitrile용매HCID 8857Ethyl Acetate용매

실험 절차

To a solution of the product of Step 1 (1.00 g, 2.43 mmol), PPh3 (1.00 g, 3.71 mmol) and diisopropylethylamine (1.3 mL, 7.28 mmol) in CH3CN (30 mL) was added hexachloroethane (0.812 g, 3.43 mmol) as a solid, portion-wise. The mixture was allowed to stir for 12 hours. TLC (3:1 hexanes:ethyl acetate) indicated the presence of starting material. Therefore, additional PPh3 (0.65 g, 2.43 mmol) and hexachloroethane (0.575 g, 2.43 mmol) were added and stirring continued for 4 hours. The solvent was removed in vacuo, the residue diluted with ethyl acetate-H2O and the layers separated. The aqueous phase was extracted twice with ethyl acetate and the combined organic layers were washed (H2O, brine), dried (Na2SO4), and filtered. The solvent was removed in vacuo and the residue purified by flash column chromatography (3:1 hexanes:ethyl acetate) to provide (S)-tert-butyl 2-(5-(4-bromophenyl)oxazol-2-yl)pyrrolidine-1-carboxylate (0.605 g, 63%). 1HNMR (400 MHz, DMSO-d6) δ 7.60-7.68 (m, 5H), 4.80-4.91 (m, 1H), 3.46-3.51 (m, 1H), 3.33-3.39 (m, 1H), 2.18-2.31 (m, 1H), 1.84-1.99 (m, 3H), 1.36 (s, 4H), 1.15 (s, 5H). LCMS: Anal. Calcd. for C18H21BrN2O3: 392. found: 393 (M+H)+.

후처리

  1. stirringstirring
  2. waitcontinued for 4 hours
  3. customThe solvent was removed in vacuo
  4. additionthe residue diluted with ethyl acetate-H2O
  5. customthe layers separated
  6. extractionThe aqueous phase was extracted twice with ethyl acetate
  7. washthe combined organic layers were washed (H2O, brine)
  8. dry with materialdried (Na2SO4)
  9. filtrationfiltered
  10. customThe solvent was removed in vacuo
  11. customthe residue purified by flash column chromatography (3:1 hexanes:ethyl acetate)

출처 및 근거

ORD 기록
ord-9549c7c3ceca4e1c87c3a408fa562cda
출처 데이터셋
uspto-grants-2010_06
특허 번호
US07741347B2

연결된 노트

불러오는 중…