Pyridine → (3S,4R)-1-(t-butyldimethylsilyl)3-[(R)-1-(t-butyldimethylsilyloxy)ethyl]-4-[3-(4-nitrobenzyl)oxycarbonyl-2-oxopropyl]azetidin-2-one

HRID 355181Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 355181
N1C=CC=CC=1.[Si:7]([N:14]1[C@H:17]([CH2:18][CH:19]([OH:34])[CH2:20][C:21]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][C:28]([N+:31]([O-:33])=[O:32])=[CH:27][CH:26]=2)=[O:22])[C@@H:16]([C@H:35]([O:37][Si:38]([C:41]([CH3:44])([CH3:43])[CH3:42])([CH3:40])[CH3:39])[CH3:36])[C:15]1=[O:45])([C:10]([CH3:13])([CH3:12])[CH3:11])([CH3:9])[CH3:8]>C(Cl)Cl.[O-2].[O-2].[O-2].[Cr+6]>[Si:7]([N:14]1[C@H:17]([CH2:18][C:19](=[O:34])[CH2:20][C:21]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][C:28]([N+:31]([O-:33])=[O:32])=[CH:27][CH:26]=2)=[O:22])[C@@H:16]([C@H:35]([O:37][Si:38]([C:41]([CH3:44])([CH3:43])[CH3:42])([CH3:39])[CH3:40])[CH3:36])[C:15]1=[O:45])([C:10]([CH3:12])([CH3:11])[CH3:13])([CH3:9])[CH3:8]

Komponenten

5

Edukt 2

HCID 1049PyridineHCID 13104637(3S,4R)-1-(t-butyldimethylsilyl)-3-[(R)-1-(t-butyldimethylsilyloxy)ethyl]-4-[3-(4-nitrobenzyl)oxycarbonyl-2-hydroxypropyl]azetidin-2-one

Produkt 1

HCID 13018175(3S,4R)-1-(t-butyldimethylsilyl)3-[(R)-1-(t-butyldimethylsilyloxy)ethyl]-4-[3-(4-nitrobenzyl)oxycarbonyl-2-oxopropyl]azetidin-2-one

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 10219390chromium (VI) trioxideKatalysatorHCID 6344DichloromethaneLösungsmittel2×

Versuchsvorschrift

Anhydrous chromium trioxide (10.0 mmol) is added to a solution of anhydrous pyridine (20.0 mmol) in 30 ml of anhydrous methylene chloride. After stirring at room temperature for 15 min., the reaction mixture is treated all at once with a solution of (3S,4R)-1-(t-butyldimethylsilyl)-3-[(R)-1-(t-butyldimethylsilyloxy)ethyl]-4-[3-(4-nitrobenzyl)oxycarbonyl-2-hydroxypropyl]-azetidin-2-one (1.00 mmol) in anhydrous methylene chloride (8 ml). The resulting mixture is stirred at room temperature for 5 min. The CH2Cl2 layer is decanted from the dark, tarry residue which is triturated with more CH2Cl2. The combined CH2Cl2 phase is concentrated in vacuo. The residue is triturated with ether (100 ml) and the ether extracts are filtered. The filtrate is washed with 5% aqueous sodium bicarbonate solution, 2.5 N HCl, 5% NaHCO3 and brine, dried over magnesium sulfate and concentrated in vacuo to yield (3S,4R)-1-(t-butyldimethylsilyl)-3-[(R)-1 -(t-butyldimethylsilyloxy)ethyl]-4-[3-(4-nitrobenzyl)oxycarbonyl-2-oxopropyl]azetidin-2-one. n.m.r. (CDCl3) δ7.85(2d-aromatic,4), δ5.27(s,2), δ4.05(m,2), δ3.6(s,2), δ2.4-3.2(dd overlapping ABq,3), δ1.2(d,3,J=6.6), δ0.9(2s,18), δ0.22(s,6), δ0.05(s,6).

Aufarbeitung

  1. stirringThe resulting mixture is stirred at room temperature for 5 min
  2. customThe CH2Cl2 layer is decanted from the dark, tarry residue which
  3. customis triturated with more CH2Cl2
  4. concentrationThe combined CH2Cl2 phase is concentrated in vacuo
  5. customThe residue is triturated with ether (100 ml)
  6. filtrationthe ether extracts are filtered
  7. washThe filtrate is washed with 5% aqueous sodium bicarbonate solution, 2.5 N HCl, 5% NaHCO3 and brine
  8. dry with materialdried over magnesium sulfate
  9. concentrationconcentrated in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-f4f6dd004621443fbca523611a764f6b
Quelldatensatz
uspto-grants-1983_03
Patentnummer
US04378315

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