Dimethyl Sulfide → (2S,3R)-3-(trityl-amino)-pentan-2-ol

HRID 1432391Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1432391
S(C)C.[CH3:4][Li].[C:6]([NH:25][C@H:26]([CH2:29][CH3:30])[CH:27]=[O:28])([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)([C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.[NH4+].[Cl-]>CCOCC.CCCCCC>[C:6]([NH:25][C@H:26]([CH2:29][CH3:30])[C@@H:27]([OH:28])[CH3:4])([C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)([C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1

Komponenten

7

Edukt 4

HCID 1068Dimethyl SulfideHCID 25517Ammonium ChlorideHCID 57714153(R)-2-(Trityl-amino)-butyraldehydeHCID 178418348HCID 178418348, Verbindung

Produkt 1

HCID 57714160(2S,3R)-3-(trityl-amino)-pentan-2-olAusbeute 91,4 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 3283Diethyl EtherLösungsmittel3×HCID 8058HexaneLösungsmittel

Versuchsvorschrift

To a stirred suspension of CuBr.SMe2 (2.74 g, 13.33 mmol) in Et2O (100 mL) under Ar e at −70° C., was added methyl lithium (1.6 M in Et2O; 16.6 mL, 26.56 mmol) dropwise and the solution allowed to warm to RT. The mixture was re-cooled to −70° C., to which was added a solution of (R)-2-(trityl-amino)-butyraldehyde (2 g, 6.05 mmol) in. Et2O (25 mL) dropwise with stirring. The reaction mixture was stirred at this temperature for 2 h, when TLC (8:2 hexane:Et2O) indicated that the reaction had gone to completion. To the reaction mixture was added a saturated aqueous solution of NH4Cl (100 mL) and allowed to warm to RT over 16 h. The reaction mixture was extracted with Et2O (2×200 mL), and the combined organic phase washed with brine (50 mL), dried (MgSO4) and evaporated in vacuo. The residue was purified by silica gel column chromatography, eluted with hexane/Et2O (8:2) to afford the title compounds as a light yellow oil (1.91 g, 91%). 1H-NMR (d6-DMSO, 250 MHz): δ 0.44-0.58 (m, 3H, —NHCH(CH2CH3)CH(CH3)OH), 0.99-1.12 (m, 5H, —NHCH (CH2CH3)CH(CH3)OH+—NHCH(CH2CH3)CH(CH3)OH), 2.03 (m, 1H, —NHCH(CH2CH3)CH(CH3)OH), 3.32-3.51 (m, 1H, —NHCH(CH2CH3)CH(CH3)OH), 4.40 (d, 1H, J=3.79 Hz, —NHCH(CH2CH3)CH(CH3)OH), 7.14-7.51 (m, 15H, 3×Bz).

Aufarbeitung

  1. temperatureThe mixture was re-cooled to −70° C., to which
  2. temperatureto warm to RT over 16 h
  3. extractionThe reaction mixture was extracted with Et2O (2×200 mL)
  4. washthe combined organic phase washed with brine (50 mL)
  5. dry with materialdried (MgSO4)
  6. customevaporated in vacuo
  7. customThe residue was purified by silica gel column chromatography
  8. washeluted with hexane/Et2O (8:2)

Quellen und Nachweise

ORD-Eintrag
ord-ff1fa55e237a40e5b82ac2db560297bc
Quelldatensatz
uspto-grants-2009_11
Patentnummer
US07612079B2

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