Diazomethane → Hexahydro-pyrrolo[3,2-b]pyrrole-1,3,4-tricarboxylic acid 1-benzyl ester 4-tert-butyl ester 3-methyl ester

HRID 446956

Reaktionsgleichung

Reaktionsgleichung von HRID 446956
[C:1]([O:5][C:6]([N:8]1[CH:15]2[CH:11]([N:12]([C:19]([O:21][CH2:22][C:23]3[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=3)=[O:20])[CH2:13][CH:14]2[C:16]([OH:18])=[O:17])[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[N+](=[CH2:31])=[N-].N(N(C)C(N)=O)=O.[OH-].[K+]>CCOC(C)=O.CCOCC>[CH3:31][O:17][C:16]([CH:14]1[CH2:13][N:12]([C:19]([O:21][CH2:22][C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)=[O:20])[CH:11]2[CH2:10][CH2:9][N:8]([C:6]([O:5][C:1]([CH3:4])([CH3:2])[CH3:3])=[O:7])[CH:15]12)=[O:18]

Komponenten

7

Edukt 4

HCID 9550DiazomethaneHCID 12699N-Methyl-N-nitrosoureaHCID 14797Potassium HydroxideHCID 67216716HCID 67216716, Verbindung

Produkt 1

HCID 67280928Hexahydro-pyrrolo[3,2-b]pyrrole-1,3,4-tricarboxylic acid 1-benzyl ester 4-tert-butyl ester 3-methyl ester

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 3283Diethyl EtherLösungsmittel2×HCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

To a solution of crude 13 (0.47 g) in EtOAc (10 mL) and Et2O (10 mL) was added an ethereal solution of diazomethane that was prepared by treatment of N-nitroso-N-methyl urea (0.5 g) in Et2O (10 mL) with 1M KOH (10 mL). After consumption of starting material (monitored by TLC), the reaction mixture was diluted with HOAc. The solution was extracted with EtOAc, washed with saturated NaHCO3, brine, dried over anhydrous Na2SO4, filtered and concentrated to give a dark oil that was purified by HPLC (2″ Dynamax® SiO2, 10% EtOAc/hexane to 100% EtOAc over 30 min) to give 14 (0.19 g) as a yellow-colored oil. 1H NMR (CDCl3, 300 MHz): δ7.40-7.29 (m, 5H), 5.23-5.09 (m, 2H), 4.56-4.52 (m, 2H), 4.11-4.04 (m, 1H), 3.69 (s, 3H), 3.45-3.42 (m, 1H), 3.22-3.12 (m, 1H), 2.27-2.10 (m, 1H), 1.96 (m, 1H), 1.47 (s, 9H) ppm. Mass spectrum, m/z [405.2] (M+H)+.

Aufarbeitung

  1. customAfter consumption of starting material (monitored by TLC)
  2. additionthe reaction mixture was diluted with HOAc
  3. extractionThe solution was extracted with EtOAc
  4. washwashed with saturated NaHCO3, brine
  5. dry with materialdried over anhydrous Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customto give a dark oil that
  9. customwas purified by HPLC (2″ Dynamax® SiO2, 10% EtOAc/hexane to 100% EtOAc over 30 min)

Quellen und Nachweise

ORD-Eintrag
ord-2c2d7ba914144c0f82a4b2f35f3aef91
Quelldatensatz
uspto-grants-2013_07
Patentnummer
US08481495B2

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