Hydrogen Peroxide → 1-(tert-Butyl) 2-methyl 4-(hydroxymethyl)pyrrolidine-1,2-dicarboxylate

HRID 71982笔记

反应方程式

HRID 71982 反应方程式
[CH3:1][O:2][C:3]([CH:5]1[CH2:9][C:8](=[CH2:10])[CH2:7][N:6]1[C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])=[O:4].[OH2:18].[OH-].[Na+].OO>C1COCC1.C(OCC)C>[CH3:1][O:2][C:3]([CH:5]1[CH2:9][CH:8]([CH2:10][OH:18])[CH2:7][N:6]1[C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])=[O:4]

参与物

7

反应物 4

HCID 784Hydrogen PeroxideHCID 962聚[6-[4-(4-氰基苯基)苯氧基]己基甲基丙烯酸酯]HCID 14798氢氧化钠HCID 592637351-(tert-Butyl) 2-methyl 4-methylenepyrrolidine-1,2-dicarboxylate

产物 1

HCID 235957531-(tert-Butyl) 2-methyl 4-(hydroxymethyl)pyrrolidine-1,2-dicarboxylate收率 41%

试剂、催化剂与溶剂 2

HCID 3283乙醚溶剂HCID 8028四氢呋喃溶剂

反应条件

温度
0 °C

实验过程

4-Methylene-pyrrolidine-1,2-dicarboxylic acid 1-tert-butyl ester 2-methyl ester (4.48 g, 19.71 mmol) was dissolved in THF (100 mL) and the stirred solution was cooled to 0° C. Borane-dimethylsulfide complex (1.9 mL, 19.7 mmol) was added and the reaction mixture was allowed to warm to RT o/n. After 16 h, water was added dropwise until no bubbling was observed. The stirred mixture was then cooled to 0° C. Aqueous NaOH (5M in H2O, 5.3 mL, 26.6 mmol), then H2O2 (30 wt % in H2O, 6.0 mL, 58.5 mmol) were added dropwise. The reaction was then warmed to 50° C. After 30 min, the mixture was diluted with ethyl ether and washed with water and brine. The organic phase was dried over MgSO4, filtered and concentrated. The crude residue was purified by silica column chromatography (25% to 75% EtOAc/Hex) to afford the title compound (2.08 g, 41%).

后处理

  1. additionBorane-dimethylsulfide complex (1.9 mL, 19.7 mmol) was added
  2. temperatureto warm to RT o/n
  3. temperatureThe stirred mixture was then cooled to 0° C
  4. temperatureThe reaction was then warmed to 50° C
  5. waitAfter 30 min
  6. washwashed with water and brine
  7. dry with materialThe organic phase was dried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe crude residue was purified by silica column chromatography (25% to 75% EtOAc/Hex)

来源与证据

ORD记录
ord-adc083c3752642d5bc7464fe75151727
来源数据集
uspto-grants-2014_09
专利号
US08822430B2

反应笔记

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