Piperidin-4-ol → Ethyl 3-cyano-3-(4-hydroxypiperidin-1-YL)pyrrolidine-1-carboxylate

HRID 1642481ノート

反応式

HRID 1642481 の反応式
[OH:1][CH:2]1[CH2:7][CH2:6][NH:5][CH2:4][CH2:3]1.O=[C:9]1[CH2:13][CH2:12][N:11]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[CH2:10]1.[C-:19]#[N:20].C([Al+]CC)C>ClCCCl.ClCCl.CC(C)[O-].[Ti+4].CC(C)[O-].CC(C)[O-].CC(C)[O-]>[C:19]([C:9]1([N:5]2[CH2:6][CH2:7][CH:2]([OH:1])[CH2:3][CH2:4]2)[CH2:13][CH2:12][N:11]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[CH2:10]1)#[N:20]

参加物

7

反応物 3

HCID 79341Piperidin-4-olHCID 277754Ethyl 3-oxopyrrolidine-1-carboxylateHCID 16686413Diethyl aluminum cyanide

生成物 1

HCID 57619828Ethyl 3-cyano-3-(4-hydroxypiperidin-1-YL)pyrrolidine-1-carboxylate収率 97.9%

試薬・触媒・溶媒 3

HCID 11026Titanium isopropoxide触媒HCID 111,2-Dichloroethane溶媒HCID 6344Dichloromethane溶媒

実験手順

To a stirred solution of 4-hydroxypiperidine (464 mg, 4.58 mmol) and ethyl 3-oxopyrrolidine-1-carboxylate (610 mg, 3.82 mmol) in 1,2-dichloroethane (25 mL) was added titanium isopropoxide (1.09 g, 3.82 mmol), and the mixture was stirred at room temperature overnight. Then a 1.0 M solution of diethylaluminum cyanide (1.02 g, 9.17 mmol) was added at room temperature and the mixture was stirred for 24 h. Diluted with dichloromethane (25 mL) and quenched with saturated ammonium chloride solution (10 mL) at 0° C. Then mixture was filtered through a small pad of celite, and the resulting filtrate was concentrated in vacuo to afford the title compound as a yellow gum (1.0 g). 1H NMR (CDCl3, 400 MHz): δ 4.22 (q, 2H), 4.21-4.1 (dd, 1H), 3.79-3.62 (m, 3H), 3.38 (dd, 1H), 2.9 (brs, 1H), 2.7 (brs, 1H), 2.54-2.35 (m, 3H), 2.18-1.85 (brm, 3H), 1.68-1.45 (m, 3H), 1.25 (t, 3H). MS (M+1): 268.14.

後処理

  1. stirringthe mixture was stirred for 24 h
  2. customquenched with saturated ammonium chloride solution (10 mL) at 0° C
  3. filtrationThen mixture was filtered through a small pad of celite
  4. concentrationthe resulting filtrate was concentrated in vacuo

出典と根拠

ORDレコード
ord-16c846a6c2334cfebe37f2a4b9414591
出典データセット
uspto-grants-2012_02
特許番号
US08119661B2

反応ノート

読み込み中…