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

HRID 18355

反応式

HRID 18355 の反応式
[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

参加物

7

反応物 4

HCID 6214Hexachloroethane2 回HCID 11776Triphenylphosphine2 回HCID 81531DiisopropylethylamineHCID 56605334(S)-tert-butyl 2-((2-(4-bromophenyl)-2-oxoethyl)carbamoyl)pyrrolidine-1-carboxylate

生成物 1

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

試薬・触媒・溶媒 2

HCID 6342Acetonitrile溶媒HCID 8857Ethyl Acetate溶媒

実験手順

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)+.

後処理

  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)

出典と根拠

ORDレコード
ord-9549c7c3ceca4e1c87c3a408fa562cda
出典データセット
uspto-grants-2010_06
特許番号
US07741347B2

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