Dimethyl Sulfide → (2r,3s)-3-(Tritylamino)pentan-2-ol

HRID 705167Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 705167
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>[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

6

Edukt 4

HCID 1068Dimethyl SulfideHCID 25517Ammonium ChlorideHCID 57452676(S)-2-(tritylamino)butanalHCID 178418348HCID 178418348, Verbindung

Produkt 1

HCID 57433109(2r,3s)-3-(Tritylamino)pentan-2-ol

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 3283Diethyl EtherLösungsmittel2×

Versuchsvorschrift

To a stirred suspension of CuBr.SMe2 (3 g, 14.6 mmol) in anhydrous ether (100 ml) under an argon atmosphere at −78° C., was added methyl lithium (1.6M in ether, 16.5 ml, 4.0 eq, 26.5 mmol) dropwise and the solution allowed to warm to room temperature over 1 h. The mixture was recooled to −78° C., and a solution of (S)-2-(trityl-amino)-butyraldehyde (2.2 g, 6.62 mmol) in ether (25 ml) was added dropwise with stirring. The reaction mixture was stirred at this temperature for 2 h then allowed to warm to room temperature over 1 h. A saturated aqueous solution of NH4Cl (50 ml) was added and the two layers separated. The organic phase was washed with brine (50 ml), dried (MgSO4) and evaporated in vacuo. The residue was purified by flash silica gel column chromatography, eluted with hexane:ethyl acetate (80:20) to afford (2R,3S)-3-(trityl-amino)-pentan-2-ol as a light yellow oil; Yield: 1.5 g (66%). (75% de 2R, 3S: 25% de 2S, 3S). 1H-NMR (d6-DMSO, 250 MHz): δ 0.0.47+0.55 (2×t, J=7.50+7.26 Hz —NHCH(CH2CH3)CH(CH3)OH), 0.99-1.12 (m, 5 H, —NHCH(CH2CH3)CH(CH3)OH), 2.01 (1 H, m, —NHCH(CH2CH3)CH(CH3)OH), 3.22-3.43 (m, 1H, —NHCH(CH2CH3)CH(CH3)OH), 4.41 [1 H, d, J=3.3, NHCH(CH2CH3)CH(CH3)OH], 7.14-7.56 (15 H, m, ArH). δC (250 MHz, CDCl3) 146.88 (C), 128.97 (6×CH), 127.83 (6×CH), 126.43 (3×CH), 71.03 (C), 68.13 (CH), 58.77 (CH), 23.09 (CH2), 17.88 (CH3), 10.47 (CH3)

Aufarbeitung

  1. customwas recooled to −78° C.
  2. stirringThe reaction mixture was stirred at this temperature for 2 h
  3. temperatureto warm to room temperature over 1 h
  4. customthe two layers separated
  5. washThe organic phase was washed with brine (50 ml)
  6. dry with materialdried (MgSO4)
  7. customevaporated in vacuo
  8. customThe residue was purified by flash silica gel column chromatography
  9. washeluted with hexane:ethyl acetate (80:20)

Quellen und Nachweise

ORD-Eintrag
ord-16a27132826e48a4bf8723b3b6cbca02
Quelldatensatz
uspto-grants-2015_11
Patentnummer
US09173938B2

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