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Citric Acid → (3S)-1-benzyloxycarbonyl-3-(tert-butoxycarbonyl)amino-4-formylpyrrolidine

HRID 1010565
ノート
印刷プレビュー

反応式

HRID 1010565 の反応式
CS(C)=O.C(Cl)(=O)C(Cl)=O.[CH2:11]([O:18][C:19]([N:21]1[CH2:25][C@H:24]([CH2:26][OH:27])[C@H:23]([NH:28][C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30])[CH2:22]1)=[O:20])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>ClCCl.C(N(CC)CC)C>[CH2:11]([O:18][C:19]([N:21]1[CH2:25][CH:24]([CH:26]=[O:27])[C@H:23]([NH:28][C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30])[CH2:22]1)=[O:20])[C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

7

反応物 4

HCID 311Citric AcidHCID 679Dimethyl SulfoxideHCID 65578Oxalyl chlorideHCID 23635905(3S,4S)-Benzyl 3-((tert-butoxycarbonyl)amino)-4-(hydroxymethyl)pyrrolidine-1-carboxylate

生成物 1

HCID 86618514(3S)-1-benzyloxycarbonyl-3-(tert-butoxycarbonyl)amino-4-formylpyrrolidine

試薬・触媒・溶媒 2

HCID 6344
Dichloromethane
溶媒
3 回
HCID 8471Triethylamine溶媒3 回

反応条件

温度
-78 °C

実験手順

Dimethyl sulfoxide (5.10 mL, 59.3 mmol) was added to a solution of oxalylchloride (5.00 mL, 57.3 mmol) in dichloromethane (100 mL), and the mixture was stirred at −78° C. for 20 minutes. Subsequently, a solution of (3S,4S)-1-benzyloxycarbonyl-3-(tert-butoxycarbonyl)amino-4-hydroxymethylpyrrolidine (8.00 g, 22.8 mmol) in dichloromethane (85 mL) was added dropwise slowly thereto, followed by stirring at the same temperature for 30 minutes, and further at −43° C. for 1 hour. Subsequently, triethylamine (30 mL) was added thereto, and the temperature of the resultant mixture was elevated to an ice cooling temperature, followed by stirring for 45 minutes. Thereafter, a 10% aqueous citric acid solution (100 mL) was added to the resultant mixture, followed by stirring for 10 minutes. The obtained aqueous layer was extracted with dichloromethane (200 mL×2). The combined organic layer was washed by saturated brine (100 mL), and dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated under reduced pressure, to thereby yield a crude aldehyde as a pale yellow oily substance. Subsequently, triethylamine (0.50 mL, 3.59 mmol) was added to a solution of the crude aldehyde compound (2.5 g, 7.18 mmol) in dichloromethane (10 mL). The resultant mixture was stirred at room temperature for 24 hours, and triethylamine (0.50 mL, 3.59 mmol) was further added thereto, followed by stirring for another 24 hours. Thereafter, silica gel (100 g) was added to the reaction mixture, followed by stirring for 24 hours. The reaction mixture was concentrated under reduced pressure, and left to stand for 24 hours. The residue was purified through silica gel column chromatography (ethyl acetate:n-hexane=7:3), to thereby yield the title compound (an isomer mixture of (4S)-form and (4R)-form (1:3)) as a colorless oily substance (750 mg, 28%).

後処理

  1. stirringby stirring at the same temperature for 30 minutes
  2. waitfurther at −43° C. for 1 hour
  3. stirringby stirring for 45 minutes
  4. stirringby stirring for 10 minutes
  5. extractionThe obtained aqueous layer was extracted with dichloromethane (200 mL×2)
  6. washThe combined organic layer was washed by saturated brine (100 mL)
  7. dry with materialdried over anhydrous sodium sulfate
  8. filtrationAfter filtration
  9. concentrationthe filtrate was concentrated under reduced pressure
  10. customto thereby yield a crude aldehyde as a pale yellow oily substance
  11. stirringby stirring for another 24 hours
  12. additionThereafter, silica gel (100 g) was added to the reaction mixture
  13. stirringby stirring for 24 hours
  14. concentrationThe reaction mixture was concentrated under reduced pressure
  15. waitleft
  16. waitto stand for 24 hours
  17. customThe residue was purified through silica gel column chromatography (ethyl acetate:n-hexane=7:3)

出典と根拠

ORDレコード
ord-e287070c2afd442d90ec9bc6883d3367
出典データセット
uspto-grants-2011_07
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US07977327B2

反応ノート

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