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

HRID 1386766ノート

反応式

HRID 1386766 の反応式
[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

参加物

5

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒3 回

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-ca371127a3f347b69c016190274631e8
出典データセット
uspto-grants-2001_07
特許番号
US06265434B1

反応ノート

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