tert-butyl(2S)-2-[4-(hydroxymethyl)-2-oxo-1-pyrrolidinyl]butanoate → 1-[(1S)-1-(tertbutoxycarbonyl)propyl]-5-oxo-3-pyrrolidinecaboxaldehyde

HRID 453249Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 453249
[OH:1][CH2:2][CH:3]1[CH2:7][N:6]([C@@H:8]([CH2:16][CH3:17])[C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[C:5](=[O:18])[CH2:4]1>C(Cl)Cl.N1C=CC=CC=1>[C:12]([O:11][C:9]([C@@H:8]([N:6]1[C:5](=[O:18])[CH2:4][CH:3]([CH:2]=[O:1])[CH2:7]1)[CH2:16][CH3:17])=[O:10])([CH3:15])([CH3:13])[CH3:14]

Komponenten

4

Edukt 1

HCID 57478730tert-butyl(2S)-2-[4-(hydroxymethyl)-2-oxo-1-pyrrolidinyl]butanoate

Produkt 1

HCID 183461161-[(1S)-1-(tertbutoxycarbonyl)propyl]-5-oxo-3-pyrrolidinecaboxaldehydeAusbeute 49,7 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 1049PyridineLösungsmittelHCID 6344DichloromethaneLösungsmittel2×

Versuchsvorschrift

In a three necked flask, under argon, a solution of tert-butyl (2S)-2-[4-(hydroxymethyl)-2-oxo-1-pyrrolidinyl]butanoate 398 (4.0 g, 0.016 mol.) in CH2Cl2 (8 ml) is added to a suspension of CrO3 (6.2 g, 0.062 mol.) in pyridine (11.3 ml)/CH2Cl2 (80 ml) stirred at room temperature. The temperature increases to 30° C. and the suspension is stirred for 0.2 h. The suspension is filtered through celite and the filtrate is washed successively with HCl 1N, brine, dried over magnesium sulfate and concentrated in vacuo to afford the crude aldehyde which is purified by column chromatography on silicagel (hexane/acetone 70/30 (v/v)) to afford 2.03 g of 1-[(1S)-1-(tertbutoxycarbonyl)propyl]-5-oxo-3-pyrrolidinecarboxaldehyde 396 (41%). Alternatively, the reaction can also be conducted with racemic ester to afford the racemic aldehyde with a similar yield. Analysis of a 1/1 mixture of 1-[(1S)-1-(tertbutoxycarbonyepropyl]-5-oxo-3-pyrrolidinecarboxaldehyde 396: 1H NMR (250 MHz, (CDCl3): 0.91 (t, 3H), 1.44 (s, 9H), 1.55-1.77 (m, 1H), 1.90-2.15 (m, 1H), 2.63-2.82 (m, 2H), 3.47-3.61 (m, 1H), 3.65-3.79 (m, 1H), 3.83-3.94 (m, 1H of one of the diastereoisomers), 4.48-4.62 (m, 1H), 9.74 (s (broad), 1H).

Aufarbeitung

  1. temperatureThe temperature increases to 30° C.
  2. stirringthe suspension is stirred for 0.2 h
  3. filtrationThe suspension is filtered through celite
  4. washthe filtrate is washed successively with HCl 1N, brine
  5. dry with materialdried over magnesium sulfate
  6. concentrationconcentrated in vacuo
  7. customto afford the crude aldehyde which
  8. customis purified by column chromatography on silicagel (hexane/acetone 70/30 (v/v))

Quellen und Nachweise

ORD-Eintrag
ord-d5133e6702c24d2c912b31a9b8d919a4
Quelldatensatz
uspto-grants-2013_07
Patentnummer
US08492416B2

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