Sodium hydride → 1-(Benzyloxycarbonyl)-4-(3-oxo-3-phenylprop-1-enyl)piperidine

HRID 1386766Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1386766
[O:1]=[C:2]([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[CH2:3]P(=O)(OCC)OCC.[H-].[Na+].[CH2:20]([O:27][C:28]([N:30]1[CH2:35][CH2:34][CH:33]([CH:36]=O)[CH2:32][CH2:31]1)=[O:29])[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1>C1COCC1>[CH2:20]([O:27][C:28]([N:30]1[CH2:35][CH2:34][CH:33]([CH:36]=[CH:3][C:2](=[O:1])[C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)[CH2:32][CH2:31]1)=[O:29])[C:21]1[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=1

Komponenten

5

Edukt 3

HCID 24758Sodium hydrideHCID 372803Diethyl 2-oxo-2-phenylethylphosphonateHCID 2776272Benzyl 4-formylpiperidine-1-carboxylate

Produkt 1

HCID 570744891-(Benzyloxycarbonyl)-4-(3-oxo-3-phenylprop-1-enyl)piperidine

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel3×

Versuchsvorschrift

Diethyl (2-oxo-2-phenylethyl)phosphonate (0.96 mL,1.1 g, 4.4 mmol) was added in one portion to a stirred suspension of sodium hydride (60% oil dispersion, 158 mg, 3.95 mmol) in THF (20 mL). After 15 min. at RT, the clear solution was cooled in an ice bath and 1-(benzyloxycarbonyl)-4-piperidinecarboxaldehyde (840 mg, 3.40 mmol) was added in THF (1.0 mL) with additional THF (2×1.0 mL) for rinsing. Stirring was continued for a total of 2 h, with slow warming to RT. The mixure was then partitioned between ether (120 ml) and 2.5 N NaOH (60 mL). The organic layer was washed with saturated aq. NaCl (60 mL), dried (Na2SO4), decanted, and evaporated. The crude product was purified by flash column chromatography on silica gel eluting with 85:15 v/v to 80:20 v/v hexanes/EtOAc to give 0-95 g of the title compound as a colorless syrup: 1H NMR (400 MHz) δ 7.82 (d, J=8, 21), 7.57 (t, J=8, 1H), 7.48 (t, J=8, 2H), 7.39-7.29 (m, 51), 6.99 (dd, J=15, 6, 1H), 6.87 (dd, J=15, 1, 1H), 5.15 (s, 2H), 2.97-2.82 (m, 2H), 2.50-2.39 (m, 1H), 1.89-1.77 (m, 2H), 1.54-1.39 (m, 2H); ESI-MS 367 (M+NH3+H).

Aufarbeitung

  1. temperaturethe clear solution was cooled in an ice bath
  2. washfor rinsing
  3. customwas continued for a total of 2 h
  4. customThe mixure was then partitioned between ether (120 ml) and 2.5 N NaOH (60 mL)
  5. washThe organic layer was washed with saturated aq. NaCl (60 mL)
  6. dry with materialdried (Na2SO4)
  7. customdecanted
  8. customevaporated
  9. customThe crude product was purified by flash column chromatography on silica gel eluting with 85:15 v/v to 80:20 v/v hexanes/EtOAc

Quellen und Nachweise

ORD-Eintrag
ord-ca371127a3f347b69c016190274631e8
Quelldatensatz
uspto-grants-2001_07
Patentnummer
US06265434B1

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