Diisopropylethylamine → (4R)-3-[(2S)-3-Methyl-1-oxo-2-[(phenylmethoxy)methyl]butyl]-4-(phenylmethyl)-2-oxazolidinone

HRID 660376Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 660376
[CH2:1]([C@@H:8]1[CH2:12][O:11][C:10](=[O:13])[N:9]1[C:14](=[O:19])[CH2:15][CH:16]([CH3:18])[CH3:17])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CCN(C(C)C)C(C)C.Cl[CH2:30][O:31][CH2:32][C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1>C(Cl)Cl.Cl[Ti](Cl)(Cl)Cl>[CH2:1]([C@@H:8]1[CH2:12][O:11][C:10](=[O:13])[N:9]1[C:14](=[O:19])[C@H:15]([CH2:30][O:31][CH2:32][C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)[CH:16]([CH3:17])[CH3:18])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Komponenten

6

Edukt 3

HCID 81531DiisopropylethylamineHCID 137983Benzyl chloromethyl etherHCID 11391340(4R)-4-Benzyl-3-(3-methylbutanoyl)-1,3-oxazolidin-2-one

Produkt 1

HCID 46741251(4R)-3-[(2S)-3-Methyl-1-oxo-2-[(phenylmethoxy)methyl]butyl]-4-(phenylmethyl)-2-oxazolidinoneAusbeute 50 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 24193Titanium TetrachlorideKatalysatorHCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

To a stirred solution of (R)-4-benzyl-3-(3-methylbutanoyl)oxazolidin-2-one (209 g, 0.80 mol) in absolute CH2Cl2 (3 L) at 0° C. under N2 was added dropwise TiCl4 (92.2 mL, 0.84 mol) over 30 min. After 15 min, DIEA (0.864 mol) was added dropwise over 15 min, and stirring was continued for 1 h at 0° C. ((Chloromethoxy)methyl)benzene (222 mL, 1.60 mol) was added dropwise over 90 min at 0° C. After stirring for 20 h at 0° C., the reaction was quenched by addition of 10% aq NH4Cl (800 mL) and H2O (1 L). The aqueous phase was extracted with CH2Cl2 (2×1 L), and the combined organic layers were washed with brine, dried over MgSO4, and concentrated. The residue was purified by flash chromatography on silica gel to afford (R)-4-benzyl-3-((S)-2-(benzyloxymethyl)-3-methylbutanoyl)oxazolidin-2-one (152 g, 50%). 1H NMR (400 MHz, CDCl3): 0.99 (m, 6H), 2.05 (m, 1H), 2.67 (m, 1H), 3.23 (m, 1H), 3.73 (m, 1H), 3.87 (m, 1H), 4.14 (m, 3H), 4.52 (m, 2H), 4.72 (m, 1H), 7.26 (m, 10H).

Aufarbeitung

  1. waitwas continued for 1 h at 0° C.
  2. stirringAfter stirring for 20 h at 0° C.
  3. customthe reaction was quenched by addition of 10% aq NH4Cl (800 mL) and H2O (1 L)
  4. extractionThe aqueous phase was extracted with CH2Cl2 (2×1 L)
  5. washthe combined organic layers were washed with brine
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated
  8. customThe residue was purified by flash chromatography on silica gel

Quellen und Nachweise

ORD-Eintrag
ord-c1ab1f0268e4472397087dbb55d55459
Quelldatensatz
uspto-grants-2011_12
Patentnummer
US08084485B2

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