Hydrogen Peroxide → 2-(R)-[2-(S)-Azidocarbonyl-1-(S)-(tert-butyl-dimethylsilanyloxy)-3-phenylpropyl]-4-(R)-fluoropyrrolidine-1-carboxylic acid tert-butyl ester

HRID 732362ノート

反応式

HRID 732362 の反応式
OO.[C:3]([O:7][C:8]([N:10]1[CH2:14][C@H:13]([F:15])[CH2:12][C@@H:11]1[C@@H:16]([O:36][Si:37]([C:40]([CH3:43])([CH3:42])[CH3:41])([CH3:39])[CH3:38])[C@H:17]([CH2:29][C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1)[C:18]([N:20]1[C@@H](C(C)C)COC1=O)=[O:19])=[O:9])([CH3:6])([CH3:5])[CH3:4].[OH-].[Li+].C(N(C(C)C)CC)(C)C.C1(P([N:69]=[N+:70]=[N-])(C2C=CC=CC=2)=O)C=CC=CC=1>C1COCC1.C(OCC)(=O)C.ClCCl.CO>[C:3]([O:7][C:8]([N:10]1[CH2:14][C@H:13]([F:15])[CH2:12][C@@H:11]1[C@@H:16]([O:36][Si:37]([C:40]([CH3:43])([CH3:42])[CH3:41])([CH3:39])[CH3:38])[C@@H:17]([C:18]([N:20]=[N+:69]=[N-:70])=[O:19])[CH2:29][C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1)=[O:9])([CH3:6])([CH3:5])[CH3:4]

参加物

10

反応物 5

HCID 784Hydrogen PeroxideHCID 3939Lithium HydroxideHCID 81531Diisopropylethylamine2 回HCID 199401P,P-Diphenylphosphinic azide2 回HCID 68815846HCID 68815846、化合物

生成物 1

HCID 866149952-(R)-[2-(S)-Azidocarbonyl-1-(S)-(tert-butyl-dimethylsilanyloxy)-3-phenylpropyl]-4-(R)-fluoropyrrolidine-1-carboxylic acid tert-butyl ester

試薬・触媒・溶媒 4

HCID 887Methanol溶媒HCID 6344Dichloromethane溶媒HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒

実験手順

Add an aqueous solution of hydrogen peroxide (30% solution, 2.7 mL, 28.1 mmol) dropwise to a solution of 2-(R)-[2-(S)-benzyl-1-(S)-(tert-butyl-dimethylsilanyloxy)-3-(4-(S)-isopropyl-2-oxo-oxazolidin-3-yl)-3-oxopropyl]-4-(R)-fluoropyrrolidine-1-carboxylic acid tert-butyl ester (2.779 g, 4.69 mmol) in THF (15 mL) at 0° C. Add 2 N lithium hydroxide (4.7 mL, 9.38 mmol) dropwise, stir 60 min and warm to room temperature. Add methanol (5 mL) and stir 18 h. Dilute with ethyl acetate and wash with 1 N HCl, saturated aqueous sodium chloride, dry (magnesium sulfate) and concentrate. Dissolve residue in dichloromethane (30 mL) and add diisopropylethylamine (1.2 mL, 7.03 mmol) followed by diphenylphosphoryl azide (1.1 mL, 5.16 mmol). Stir 1 h and add diisopropylethylamine (1.2 mL, 7.03 mmol) followed by diphenylphosphoryl azide (1.1 mL, 5.16 mmol). Stir 3.5 h, concentrate and purify (silica gel chromatography, eluting with hexanes and ethyl acetate) to give the title compound as a residue (0.79 g, 32%).

後処理

  1. washwash with 1 N HCl, saturated aqueous sodium chloride
  2. dry with materialdry (magnesium sulfate)
  3. concentrationconcentrate
  4. stirringStir 1 h
  5. stirringStir 3.5 h
  6. concentrationconcentrate
  7. custompurify
  8. wash(silica gel chromatography, eluting with hexanes and ethyl acetate)

出典と根拠

ORDレコード
ord-f0673f141eee4e1480193d864ffbc8c2
出典データセット
uspto-grants-2009_09
特許番号
US07585885B2

反応ノート

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