4-Methoxybenzaldehyde → 1-Tert-butyl 4-methyl 4-((4-methoxybenzylamino)methyl)piperidine-1,4-dicarboxylate

HRID 513094ノート

反応式

HRID 513094 の反応式
[NH2:1][CH2:2][C:3]1([C:16]([O:18][CH3:19])=[O:17])[CH2:8][CH2:7][N:6]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH2:5][CH2:4]1.[CH3:20][O:21][C:22]1[CH:29]=[CH:28][C:25]([CH:26]=O)=[CH:24][CH:23]=1.C([BH3-])#N.[Na+]>CO>[CH3:20][O:21][C:22]1[CH:29]=[CH:28][C:25]([CH2:26][NH:1][CH2:2][C:3]2([C:16]([O:18][CH3:19])=[O:17])[CH2:4][CH2:5][N:6]([C:9]([O:11][C:12]([CH3:14])([CH3:15])[CH3:13])=[O:10])[CH2:7][CH2:8]2)=[CH:24][CH:23]=1

参加物

5

反応物 3

HCID 312444-MethoxybenzaldehydeHCID 5003444Sodium cyanoborohydrideHCID 254188221-tert-Butyl 4-methyl 4-(aminomethyl)piperidine-1,4-dicarboxylate

生成物 1

HCID 683146401-Tert-butyl 4-methyl 4-((4-methoxybenzylamino)methyl)piperidine-1,4-dicarboxylate収率 58%

試薬・触媒・溶媒 1

HCID 887Methanol溶媒

反応条件

温度
45 °C

実験手順

Commercial available 1-tert-butyl 4-methyl 4-(aminomethyl)piperidine-1,4-dicarboxylate (10.10 mmol, 2.75 g) and 4-methoxybenzaldehyde (15.15 mmol, 2.062 g) in anhydrous MeOH (40 mL) were stirred for 2 h at rt. After addition of sodium cyanoborohydride (20.19 mmol, 1.269 g) the reaction was stirred overnight at 45° C. The mixture was evaporated in vacuo, and solved in EtOAc and sat. aq. bicarb. After separation of the organic phase, the aq. phase was extracted with EtOAc. The combined organic phase was dried over MgSO4 and evaporated in vacuo. The crude was purified by flash chromatography (heptane/EtOAc: 10 to 100%) yielding 2.3 g oil (58%). 1H NMR (400 MHz, CDCl3, 300K): δ=1.40 (2H, s), 1.45 (9H, s), 2.07 (2H, dt, J=13.3 Hz, J=3.4 Hz), 2.66 (2H, m), 2.94 (2H, m), 3.68 (2H, s), 3.70 (3H, s), 3.76 (2H, m), 3.79 (3H, s), 6.85 (2H, d, J=8.3 Hz), 7.19 (2H, d, J=8.3 Hz). 13C NMR (100 MHz, CDCl3, 300K): δ=28.8, 31.9, 47.3, 52.3, 53.9, 55.7, 57.3, 79.8, 114.0, 129.4, 132.8, 155.2, 159.0, 176.1. MS (ES) C21H32N2O5 requires: 392. found: 393.3 [M+H]+.

後処理

  1. customThe mixture was evaporated in vacuo
  2. customAfter separation of the organic phase
  3. extractionthe aq. phase was extracted with EtOAc
  4. dry with materialThe combined organic phase was dried over MgSO4
  5. customevaporated in vacuo
  6. customThe crude was purified by flash chromatography (heptane/EtOAc: 10 to 100%)

出典と根拠

ORDレコード
ord-9da0949fd8e9494597b34ceeb3fb6231
出典データセット
uspto-grants-2015_08
特許番号
US09102676B2

反応ノート

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