Trimethyl orthoformate → 1-Boc-3-(3-oxo-1-piperazinyl)azetidine

HRID 1945509Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1945509
[NH:1]1[CH2:6][CH2:5][NH:4][CH2:3][C:2]1=[O:7].[C:8]([O:12][C:13]([N:15]1[CH2:18][C:17](=O)[CH2:16]1)=[O:14])([CH3:11])([CH3:10])[CH3:9].C(OC)(OC)OC.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C>CC(O)=O.ClCCCl>[C:8]([O:12][C:13]([N:15]1[CH2:18][CH:17]([N:4]2[CH2:5][CH2:6][NH:1][C:2](=[O:7])[CH2:3]2)[CH2:16]1)=[O:14])([CH3:11])([CH3:9])[CH3:10]

Komponenten

7

Edukt 4

HCID 9005Trimethyl orthoformateHCID 231360Piperazin-2-oneHCID 15194043-Oxo-azetidine-1-carboxylic acid tert-butyl esterHCID 2724942Triacetoxyborohydride

Produkt 1

HCID 596054391-Boc-3-(3-oxo-1-piperazinyl)azetidineAusbeute 28 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 111,2-DichloroethaneLösungsmittelHCID 176Acetic AcidLösungsmittel

Versuchsvorschrift

A mixture of piperazin-2-one (1.52 g, 15.1 mmol), 3-oxoazetidine-1-carboxylic acid tert-butyl ester (2.0 g, 11.6 mmol) and trimethyl orthoformate (12.8 mL, 12.4 g, 117 mmol) in AcOH (0.7 mL) and DCE (50 mL) was stirred for 5 h before the addition of triacetoxyborohydride (4.9 g, 23.2 mmol). The resulting mixture was stirred for 16 h then partitioned between DCM and H2O. The organic layer was dried (Na2SO4) and concentrated in vacuo. The resulting oil was purified by column chromatography (Si—PCC, MeOH:DCM, 0-10%) affording the title compound as a foam (827 mg, 28%). 1H NMR (CDCl3, 300 MHz): δ 6.24 (s, 1 H); 3.97 (dd, J=8.9, 7.1 Hz, 2 H); 3.82 (dd, J=5.2, 2.2 Hz, 2 H); 3.40 (td, J=5.2, 2.2 Hz, 2 H); 3.24-3.15 (m, 1 H); 3.07 (s, 2 H); 2.60 (t, J=5.4 Hz, 2 H); 1.44 (s, 9 H).

Aufarbeitung

  1. customthen partitioned between DCM and H2O
  2. dry with materialThe organic layer was dried (Na2SO4)
  3. concentrationconcentrated in vacuo
  4. customThe resulting oil was purified by column chromatography (Si—PCC, MeOH:DCM, 0-10%)

Quellen und Nachweise

ORD-Eintrag
ord-59f6b54711544d30a4619d155b519d5a
Quelldatensatz
uspto-grants-2013_03
Patentnummer
US08394796B2

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