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

HRID 417632Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 417632
[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]

Komponenten

7

Edukt 4

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 887MethanolLösungsmittelHCID 962WaterLösungsmittel

Versuchsvorschrift

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%).

Aufarbeitung

  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)

Quellen und Nachweise

ORD-Eintrag
ord-03022e5ed1b640beb2932584f5b8f70c
Quelldatensatz
uspto-grants-2012_01
Patentnummer
US08088368B2

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