Dichloromethane → (4R,5S)-4-Methyl-3-((R)-4-methyl-octanoyl)-5-phenyl-oxazolidin-2-one

HRID 458038ノート

反応式

HRID 458038 の反応式
[CH3:1][C@H:2]([CH2:8][CH2:9][CH2:10][CH3:11])[CH2:3][CH2:4][C:5]([OH:7])=O.[C:12](Cl)(=[O:16])[C:13](Cl)=O.[O:18]1[CH2:22][CH2:21][NH:20][C:19]1=O.[CH2:24]([Li])[CH2:25][CH2:26][CH3:27].[CH2:29](Cl)Cl>CN(C=O)C.C1COCC1>[CH3:22][C@@H:21]1[C@H:12]([C:13]2[CH:29]=[CH:24][CH:25]=[CH:26][CH:27]=2)[O:16][C:19](=[O:18])[N:20]1[C:5](=[O:7])[CH2:4][CH2:3][C@H:2]([CH3:1])[CH2:8][CH2:9][CH2:10][CH3:11]

参加物

8

反応物 5

HCID 6344DichloromethaneHCID 65578Oxalyl chlorideHCID 739492-OxazolidinoneHCID 6997333(4R)-4-methyloctanoic acidHCID 178418339Butyllithium

生成物 1

HCID 57142278(4R,5S)-4-Methyl-3-((R)-4-methyl-octanoyl)-5-phenyl-oxazolidin-2-one

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide触媒HCID 8028Tetrahydrofuran溶媒2 回

実験手順

To acid 136 (2.14 g, 13.5 mmol) in 25 mL CH2Cl2 at 0° C. was added 3 drops DMF, followed by oxalyl chloride (1.42 mL, 16.2 mmol) resulting in vigorous gas evolution. The solution was warmed directly to ambient temperature, stirred 30 minutes, and concentrated. Meanwhile, to a solution of the oxazolidinone (2.64 g, 14.9 mmol) in 40 mL THF at −78° C. was added n-butyl lithium (1.6 M solution in hexanes, 9.3 mL, 14.9 mmol) dropwise. The mixture was stirred for 10 minutes at which time the acid chloride in 10 mL THF was added dropwise. The reaction was stirred 30 minutes at −78° C., then warmed directly to ambient temperature and quenched with sat. NH4Cl. The mixture was partitioned between Et2O and sat. NH4Cl (aq), the phases were separated, and the organic phase dried (MgSO4), and concentrated to furnish 3.2 g of oxazolidinone 137 as a colorless oil. LRMS: m/z 318.2 (M+); 1H NMR (CDCl3): δ 7.34 (m, 5H), 5.64 (d, J=7.3 Hz, 1H), 4.73 (quint, J=6.8 Hz, 1H), 2.96 (m, 1H), 2.86 (m, 1H), 1.66 (m, 1H), 1.47 (m, 2H), 1.26 (m, 5H), 1.13 (m, 1H), 0.88 (m, 9H). The crude product was used without purification.

後処理

  1. customresulting in vigorous gas evolution
  2. concentrationconcentrated
  3. additionwas added dropwise
  4. stirringThe reaction was stirred 30 minutes at −78° C.
  5. temperaturewarmed directly to ambient temperature
  6. customquenched with sat. NH4Cl
  7. customThe mixture was partitioned between Et2O and sat. NH4Cl (aq)
  8. customthe phases were separated
  9. dry with materialthe organic phase dried (MgSO4)
  10. concentrationconcentrated

出典と根拠

ORDレコード
ord-4d6e3875113940dcb16d80f91373419b
出典データセット
uspto-grants-2007_03
特許番号
US07189747B2

反応ノート

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