Benzyl chloroformate → O1-benzyl O2-methyl 4-methylenepyrrolidine-1,2-dicarboxylate

HRID 79885ノート

反応式

HRID 79885 の反応式
[C:1]([O:5][C:6]([N:8]1[CH2:12][C:11](=[CH2:13])[CH2:10][CH:9]1[C:14]([OH:16])=[O:15])=[O:7])([CH3:4])(C)C.Cl.O1CCOC[CH2:19]1.CCN(C(C)C)C(C)C.C(OC(Cl)=O)[C:34]1[CH:39]=[CH:38]C=[CH:36][CH:35]=1>CO.O>[CH3:19][O:16][C:14]([CH:9]1[CH2:10][C:11](=[CH2:13])[CH2:12][N:8]1[C:6]([O:5][CH2:1][C:4]1[CH:38]=[CH:39][CH:34]=[CH:35][CH:36]=1)=[O:7])=[O:15]

参加物

7

反応物 4

HCID 10387Benzyl chloroformateHCID 81531DiisopropylethylamineHCID 204431481,4-Dioxane hydrochlorideHCID 217625641-(tert-Butoxycarbonyl)-4-methylenepyrrolidine-2-carboxylic acid

生成物 1

HCID 21922647O1-benzyl O2-methyl 4-methylenepyrrolidine-1,2-dicarboxylate収率 56%

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 962Water溶媒

実験手順

4-Methylene-pyrrolidine-1,2-dicarboxylic acid 1-tert-butyl ester (12.00 g, 52.80 mmol) was dissolved in MeOH (200 mL) and treated with 4.0 M HCl/dioxane (50 mL). After stirring for 3.5 hours at room temperature, the reaction mixture was concentrated under reduced pressure. The crude residue was dissolved in DCM (200 mL) and treated with DIPEA (22 mL, 127 mmol) and BnOCOCl (9.64 mL, 63.4 mmol). After stirring for 1 hours at room temperature, the reaction mixture was poured into H2O. The aqueous layer was extracted 3× with DCM. The combined organics were dried over MgSO4, filtered and concentrated. The residue was purified by silica column chromatography (10% to 25% EtOAc/hexane) to provide 4-Methylene-pyrrolidine-1,2-dicarboxylic acid 1-benzyl ester 2-methyl ester (8.20 g, 56%).

後処理

  1. concentrationthe reaction mixture was concentrated under reduced pressure
  2. dissolutionThe crude residue was dissolved in DCM (200 mL)
  3. stirringAfter stirring for 1 hours at room temperature
  4. extractionThe aqueous layer was extracted 3× with DCM
  5. dry with materialThe combined organics were dried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified by silica column chromatography (10% to 25% EtOAc/hexane)

出典と根拠

ORDレコード
ord-a91308c89c7240a28b622a00cc69d337
出典データセット
uspto-grants-2014_09
特許番号
US08841278B2

反応ノート

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