Acetic Acid → (2S,4S)4-acetoxy-1-tert-butoxycarbonyl-2-tert-butyldiphenylsilyloxymethypyrrolidine

HRID 350487Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 350487
[C:1]([O:5][C:6]([N:8]1[CH2:12][C@H:11]([OH:13])[CH2:10][C@H:9]1[CH2:14][O:15][Si:16]([C:29]([CH3:32])([CH3:31])[CH3:30])([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[C:33](O)(=[O:35])[CH3:34].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1>[C:33]([O:13][C@@H:11]1[CH2:12][N:8]([C:6]([O:5][C:1]([CH3:4])([CH3:2])[CH3:3])=[O:7])[C@H:9]([CH2:14][O:15][Si:16]([C:29]([CH3:32])([CH3:31])[CH3:30])([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)[C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)[CH2:10]1)(=[O:35])[CH3:34]

Komponenten

6

Edukt 4

HCID 176Acetic AcidHCID 11776TriphenylphosphineHCID 5363146Diisopropyl azodicarboxylateHCID 69332404HCID 69332404, Verbindung

Produkt 1

HCID 69340895(2S,4S)4-acetoxy-1-tert-butoxycarbonyl-2-tert-butyldiphenylsilyloxymethypyrrolidineAusbeute 99 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
50 °C

Versuchsvorschrift

To a stirred mixture of (2S,4R)-1-tert-butoxycarbonyl-2-tert-butyldiphenylsilyloxymethy-4-hydroxypyrrolidine (21.7 g, 47.6 mmol), acetic acid (3.0 ml, 52.4 mmol) and PPh3 (12.5 g, 52.4 mmol) in THF (330 ml) was added DIAD (9.4 ml, 47.6 mmol) at room temperature under an atmosphere of nitrogen. After 2 h stirring the same temperature, the mixture was heated at 50° C. for 2 h . After cooling to room temperature, the reaction mixture was concentrated in vacuo. The resulting residue was chromatographed on silica gel [1 Kg, n-hexane/EtOAc(5/1)], to give (2S,4S)4-acetoxy-1-tert-butoxycarbonyl-2-tert-butyldiphenylsilyloxymethypyrrolidine (23.3 g, 99%) as a colorless oil. 1H-NMR (CDCl3) δ 1.06 (s, 9H), 1.35 and 1.43 (s, 9H, amide isomers), 1.92 (br, 3H), 2.20–2.45 (m, 2H), 3.31–4.07 (m, 5H), 5.17–5.30 (m, 1H), 7.36–7.44 (m, 6H), 7.65–7.71 (m, 4H).

Aufarbeitung

  1. temperatureAfter cooling to room temperature
  2. concentrationthe reaction mixture was concentrated in vacuo
  3. customThe resulting residue was chromatographed on silica gel [1 Kg, n-hexane/EtOAc(5/1)]

Quellen und Nachweise

ORD-Eintrag
ord-987a225b992b4101a7fffd1f417fc61c
Quelldatensatz
uspto-grants-2007_02
Patentnummer
US07179819B2

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