Diethyl (cyanomethyl)phosphonate → Tert-butyl 4-(3-cyanoprop-2-en-1-yl)piperidine-1-carboxylate

HRID 1876841ノート

反応式

HRID 1876841 の反応式
CC(C)([O-])C.[K+].[C:7]([CH2:9]P(=O)(OCC)OCC)#[N:8].O=[CH:19][CH2:20][CH:21]1[CH2:26][CH2:25][N:24]([C:27]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])[CH2:23][CH2:22]1>O1CCCC1>[C:7]([CH:9]=[CH:19][CH2:20][CH:21]1[CH2:26][CH2:25][N:24]([C:27]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])[CH2:23][CH2:22]1)#[N:8]

参加物

5

反応物 3

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 10353694tert-Butyl 4-(2-oxoethyl)piperidine-1-carboxylateHCID 23665647Potassium tert-butoxide

生成物 1

HCID 67155885Tert-butyl 4-(3-cyanoprop-2-en-1-yl)piperidine-1-carboxylate収率 75.3%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒3 回

実験手順

To a solution of 1.0 M of potassium tert-butoxide in tetrahydrofuran (45.8 mL) at 0° C. was added dropwise a solution of diethyl cyanomethylphosphonate (7.77 mL, 0.0480 mol) in tetrahydrofuran (58.39 mL). The reaction was warmed to room temperature and then cooled at 0° C. again. To the reaction mixture was added a solution of tert-butyl 4-(2-oxoethyl)piperidine-1-carboxylate (9.91 g, 0.0436 mol) in tetrahydrofuran (11.7 mL). The reaction was allowed to warm up to room temperature and stirred at room temperature overnight. After being quenched with water, the mixture was extracted with EtOAc. The combined organic layers were washed with brine, dried and evaporated to dryness. The crude mixture was purified on silica gel, eluting with 0 to 40% EtOAc in hexanes, to give the desired product (8.22 g, 75% in 2 steps). LCMS (M+Na) 273.0.

後処理

  1. temperaturecooled at 0° C. again
  2. temperatureto warm up to room temperature
  3. customAfter being quenched with water
  4. extractionthe mixture was extracted with EtOAc
  5. washThe combined organic layers were washed with brine
  6. customdried
  7. customevaporated to dryness
  8. customThe crude mixture was purified on silica gel
  9. washeluting with 0 to 40% EtOAc in hexanes

出典と根拠

ORDレコード
ord-61f9ed2b28bd4621b70b36aae1e70578
出典データセット
uspto-grants-2012_11
特許番号
US08309718B2

反応ノート

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