Sodium hydride → (S)-1-tert-Butyl 2-methyl 4-(cyanomethylene)pyrrolidine-1,2-dicarboxylate

HRID 457907Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 457907
CCOP(OCC)([CH2:6][C:7]#[N:8])=O.[H-].[Na+].O=[C:15]1[CH2:19][N:18]([C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[C@H:17]([C:27]([O:29][CH3:30])=[O:28])[CH2:16]1.[Cl-].[NH4+]>C1COCC1.C(OCC)(=O)C>[C:7]([CH:6]=[C:15]1[CH2:19][N:18]([C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[C@H:17]([C:27]([O:29][CH3:30])=[O:28])[CH2:16]1)#[N:8]

Komponenten

7

Edukt 4

HCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 75676Diethyl (cyanomethyl)phosphonateHCID 109884851-tert-butyl 2-methyl (2S)-4-oxopyrrolidine-1,2-dicarboxylate

Produkt 1

HCID 118308474(S)-1-tert-Butyl 2-methyl 4-(cyanomethylene)pyrrolidine-1,2-dicarboxylateAusbeute 80 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8028TetrahydrofuranLösungsmittel2×HCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

Diethyl cyanomethyl phosphonate (0.86 ml, 4.4 mmol) was dissolved in dry THF (50 ml) and the solution cooled to 0° C. Sodium hydride (205 mg of a 60% suspension in parrafin oil, 5.1 mmol) was then added cautiously and the reaction stirred for 30 min. The reaction mixture was then cooled to −78° C. and a solution of 1-tert-butyl 2-methyl (2S)-4-oxo-1,2-pyrrolidinedicarboxylate (1.0 g, 4.1 mmol) in dry THF (5 ml) was added dropwise. The reaction was then allowed to reach room temperature. Saturated aqueous ammonium chloride solution (15 ml) was then added, followed by ethyl acetate (100 ml). (The organic layer was removed, and the aqueous washed with ethyl acetate (3×5 ml). The combined organic layers were dried with brine and magnesium sulfate before filtering and removal of solvent. Silica gel chromatography, eluting with 35% ethyl acetate in hexanes gave the desired compound (860 mg, 80%) as an off-white wax.

Aufarbeitung

  1. temperatureThe reaction mixture was then cooled to −78° C.
  2. customto reach room temperature
  3. custom(The organic layer was removed
  4. washthe aqueous washed with ethyl acetate (3×5 ml)
  5. dry with materialThe combined organic layers were dried with brine and magnesium sulfate
  6. filtrationbefore filtering
  7. customremoval of solvent
  8. washSilica gel chromatography, eluting with 35% ethyl acetate in hexanes

Quellen und Nachweise

ORD-Eintrag
ord-932ddb79035e4cdfa8c492c9c8def126
Quelldatensatz
uspto-grants-2007_03
Patentnummer
US07189754B2

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