Diisopropylethylamine → (R)-tert-butyl 4-((1R,2R)-3-((R)-4-benzyl-2-oxooxazolidin-3-yl)-1-hydroxy-2-methyl-3-oxopropyl)-2,2-dimethyloxazolidine-3-carboxylate

HRID 924423Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 924423
[O:1]=[C:2]([N:5]1[C@H:9]([CH2:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[CH2:8][O:7][C:6]1=[O:17])[CH2:3][CH3:4].CCN(C(C)C)C(C)C.[CH:27]([C@H:29]1[CH2:33][O:32][C:31]([CH3:35])([CH3:34])[N:30]1[C:36]([O:38][C:39]([CH3:42])([CH3:41])[CH3:40])=[O:37])=[O:28]>C(Cl)Cl.Cl[Ti](Cl)(Cl)Cl>[CH2:10]([C@@H:9]1[CH2:8][O:7][C:6](=[O:17])[N:5]1[C:2](=[O:1])[C@H:3]([CH3:4])[C@H:27]([C@H:29]1[CH2:33][O:32][C:31]([CH3:35])([CH3:34])[N:30]1[C:36]([O:38][C:39]([CH3:42])([CH3:41])[CH3:40])=[O:37])[OH:28])[C:11]1[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=1

Komponenten

6

Edukt 3

HCID 81531DiisopropylethylamineHCID 1787923-Boc-2,2-dimethyloxazolidine-4-carboxaldehyde, (R)-(+)-HCID 10966403(R)-(-)-4-Benzyl-3-propionyl-2-oxazolidinone

Produkt 1

HCID 11953594(R)-tert-butyl 4-((1R,2R)-3-((R)-4-benzyl-2-oxooxazolidin-3-yl)-1-hydroxy-2-methyl-3-oxopropyl)-2,2-dimethyloxazolidine-3-carboxylateAusbeute 87 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 24193Titanium TetrachlorideKatalysatorHCID 6344DichloromethaneLösungsmittel3×

Reaktionsbedingungen

Temperatur
-40 °C

Versuchsvorschrift

To a solution of (R)-3-(1-oxopropyl)-4-benzyl-2-oxazolidinone (Aldrich, 2.0 g, 8.6 mmol) in DCM (60 mL) at −40° C., a solution of TiCl4 in DCM (1.0 M, 10.0 mL, 10.0 mmol) was added. The mixture was stirred at −40° C. for 10 min., then DIPEA (3.7 mL, 21 mmol) was added. The reaction mixture was allowed to warm to 0° C. and stirred for 20 min. A solution of tert-butyl (4R)-4-formyl-2,2-dimethyl-1,3-oxazolidine-3-carboxylate (Aldrich, 2.0 g, 8.7 mmol) in DCM (20 mL) was then added dropwise and the resulting mixture was stirred for 1.5 h. The reaction was quenched by the addition of a saturated aq. NH4Cl and the mixture was extracted with EtOAc. The separated organic phase was washed with brine, dried over MgSO4, and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (eluting with 0-40% EtOAc in hexanes) to give the sub-title compound as the major product (5:2) in 87% yield (3.44 g). LCMS calc. for C24H34N2NaO7 (M+Na)+: m/z=485.2. found 485.1.

Aufarbeitung

  1. temperatureto warm to 0° C.
  2. stirringstirred for 20 min
  3. stirringthe resulting mixture was stirred for 1.5 h
  4. customThe reaction was quenched by the addition of a saturated aq. NH4Cl
  5. extractionthe mixture was extracted with EtOAc
  6. washThe separated organic phase was washed with brine
  7. dry with materialdried over MgSO4
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was purified by flash chromatography on silica gel (eluting with 0-40% EtOAc in hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-7f92c3eda3d34da88ce16e1b4ef0f2a9
Quelldatensatz
uspto-grants-2016_03
Patentnummer
US09278950B2

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