4-Vinylpyridine → 5-(2-(4-Pyridinyl)ethenyl)-6-chloro-3-(1-BOC-2-(S)-azetidinylmethoxy)pyridine

HRID 1780361ノート

反応式

HRID 1780361 の反応式
Br[C:2]1[CH:3]=[C:4]([O:9][CH2:10][C@@H:11]2[CH2:14][CH2:13][N:12]2[C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH:5]=[N:6][C:7]=1[Cl:8].[CH:22]([C:24]1[CH:29]=[CH:28][N:27]=[CH:26][CH:25]=1)=[CH2:23].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(N(CC)CC)C>C(#N)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[N:27]1[CH:28]=[CH:29][C:24]([CH:22]=[CH:23][C:2]2[CH:3]=[C:4]([O:9][CH2:10][C@@H:11]3[CH2:14][CH2:13][N:12]3[C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[CH:5]=[N:6][C:7]=2[Cl:8])=[CH:25][CH:26]=1

参加物

7

反応物 4

HCID 75024-VinylpyridineHCID 8471TriethylamineHCID 80271Tri-o-tolylphosphineHCID 228726673-(1-BOC-2-(S)-azetidinylmethoxy)-5-bromo-6-chloropyridine

生成物 1

HCID 538519835-(2-(4-Pyridinyl)ethenyl)-6-chloro-3-(1-BOC-2-(S)-azetidinylmethoxy)pyridine収率 35%

試薬・触媒・溶媒 2

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

実験手順

To a solution of 5-bromo-6-chloro-3-(1-BOC-2-(S)-azetidinylmethoxy)pyridine from Example 66a (470 mg, 1.25 mmol) in acetonitrile (6.2 mL) was added 4-vinylpyridine (0.17 mL, 1.57 mmol), palladium acetate (26.0 mg, 0.11 mmol), tri-o-tolylphosphine (130 mg, 0.1 mmol) and triethylamine (2.6 mL). The reaction mixture was heated at reflux overnight, then cooled to room temperature. The solvent was removed, and the residue was chromatographed on a silica gel column, eluting with ethyl acetate:hexane 1:1 to 3:1 to afford the title compound (176 mg, 35% yield). MS (CI/NH3) m/z 402 (M+H)+. 1H NMR (CDCl3, 300 MHz) δ1.42 (s, 9H), 2.27-2.43 (m, 2H), 3.86-3.95 (m, 2H), 4.27-4.24 (m, 1H), 4.36-4.67 (m, 1H), 4.50-4.60 (m, 1H), 7.07 (d, J=11, 1H), 7.41-7.47 (m, 4H), 7.57 (d, J=11, 1H), 7.58-7.65 (m, 1H), 8.09 (d, J=2, 1H), 8.61-8.68 (m, 2H).

後処理

  1. temperatureThe reaction mixture was heated
  2. temperatureat reflux overnight
  3. customThe solvent was removed
  4. customthe residue was chromatographed on a silica gel column
  5. washeluting with ethyl acetate:hexane 1:1 to 3:1

出典と根拠

ORDレコード
ord-6381875492d74e8381a8778f5b01aa4c
出典データセット
uspto-grants-1997_05
特許番号
US05629325

反応ノート

読み込み中…