Acetic acid--water (1/1) → (S)-di-tert-butyl-5-formylpyrrolidine-1,2-dicarboxylate

HRID 594832

反応式

HRID 594832 の反応式
[C:1]([O:5][C:6]([N:8]1[C@H:12]([C:13]#N)[CH2:11][CH2:10][C@H:9]1[C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])=[O:7])([CH3:4])([CH3:3])[CH3:2].CC(O)=[O:24].O>[Ni].O.O>[C:1]([O:5][C:6]([N:8]1[C@H:12]([CH:13]=[O:24])[CH2:11][CH2:10][C@H:9]1[C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])=[O:7])([CH3:4])([CH3:3])[CH3:2]

参加物

5

反応物 2

HCID 21899381Acetic acid--water (1/1)HCID 131734566(S)-di-tert-butyl-5-cyanopyrrolidine-1,2-dicarboxylate

生成物 1

HCID 131734565(S)-di-tert-butyl-5-formylpyrrolidine-1,2-dicarboxylate収率 51%

試薬・触媒・溶媒 2

HCID 444642Hydroxy-nickel触媒HCID 962Water溶媒

反応条件

温度
80 °C

実験手順

90 g Raney-Ni/H2O (50 w % in water, Acros) was added to a solution of 17.905 g (60.42 mmol) of the cyanide 110 in 640 ml Py/AcOH/H2O (2:1:1) and stirred under hydrogen for 72 h at 80° C. 300 ml water was added to the suspension, and the suspension was extracted 3× with 800 ml MTBE each. The combined organic phases were washed twice with water, dried over magnesium sulfate, and the solvent was removed at reduced pressure. The residue was filtered with 1000 ml EtOAc/CyHex (1:1) over silica gel, and, following the removal of the solvent, the raw product was purified by chromatography on silica gel with EtOAc/CyHex 1:4 as eluent. 9.234 g (30.85 mmol, 51%) of the aldehyde 111 was obtained as yellow oil (d.r.: 1.7:1 cis:trans).

後処理

  1. extractionthe suspension was extracted 3× with 800 ml MTBE each
  2. washThe combined organic phases were washed twice with water
  3. dry with materialdried over magnesium sulfate
  4. customthe solvent was removed at reduced pressure
  5. filtrationThe residue was filtered with 1000 ml EtOAc/CyHex (1:1) over silica gel
  6. customthe removal of the solvent
  7. customthe raw product was purified by chromatography on silica gel with EtOAc/CyHex 1:4 as eluent

出典と根拠

ORDレコード
ord-4dbdd949243b43deaf76b6a27f3f2494
出典データセット
uspto-grants-2016_01
特許番号
US09242985B2

関連ノート

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