Triethylamine → HCID 68160224、化合物

HRID 537350ノート

反応式

HRID 537350 の反応式
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1([C:21]#[N:22])[CH2:13][CH2:12][N:11]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:10][CH2:9]1.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.CCN(CC)CC.[CH2:52]([O:54][C:55](=[O:58])[CH:56]=[CH2:57])[CH3:53]>CC([O-])=O.CC([O-])=O.[Pd+2].CC#N>[C:21]([C:8]1([C:3]2[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=2/[CH:57]=[CH:56]/[C:55]([O:54][CH2:52][CH3:53])=[O:58])[CH2:13][CH2:12][N:11]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:10][CH2:9]1)#[N:22]

参加物

7

反応物 4

HCID 8471TriethylamineHCID 8821Ethyl AcrylateHCID 80271Tri-o-tolylphosphineHCID 49760259tert-Butyl 4-(2-bromophenyl)-4-cyanopiperidine-1-carboxylate

生成物 1

HCID 68160224HCID 68160224、化合物収率 96%

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 6342Acetonitrile溶媒

反応条件

温度
85 °C

実験手順

Tert-butyl 4-(2-bromophenyl)-4-cyanopiperidine-1-carboxylate (20, 100 mg, 0.28 mmol) and Pd(OAc)2 (7.0 mg, 0.030 mmol) were added to a vial, followed by tri(o-tolyl)phosphine (14 mg, 0.047 mmol). The reaction vial was purged with Ar (3×). Dry CH3CN (1.4 mL) and Et3N (103 μL, 0.74 mmol) were added, followed by ethylacrylate (36 μL, 0.33 mmol). The reaction mixture was heated at 85° C. overnight. The reaction was concentrated. Et2O (2 mL) was added to the mixture and was then filtered through Celite. The crude residue was purified by silica gel chromatography (gradient, 10% to 20% EtOAc/hexanes) to yield (E)-tert-butyl 4-cyano-4-(2-(3-ethoxy-3-oxoprop-1-enyl)phenyl)piperidine-1-carboxylate as a pale yellow oil (21, 102 mg, 96% yield). 1H NMR (400 MHz, CDCl3): δ 8.51 (d, 1H), 7.58 (dd, 1H), 7.41 (td, 1H), 7.38-7.34 (m, 1H), 6.31 (d, 1H), 4.29 (q, 1H), 3.29 (bt, 2H), 2.35-2.31 (m, 2H), 1.90 (dt, 2H), 1.47 (s, 9H), 1.35 (t, 3H).

後処理

  1. customThe reaction
  2. customvial was purged with Ar (3×)
  3. concentrationThe reaction was concentrated
  4. additionEt2O (2 mL) was added to the mixture
  5. filtrationwas then filtered through Celite
  6. customThe crude residue was purified by silica gel chromatography (gradient, 10% to 20% EtOAc/hexanes)

出典と根拠

ORDレコード
ord-3e33360a79a447a293d4b8e230160e28
出典データセット
uspto-grants-2014_10
特許番号
US08859776B2

反応ノート

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