Cesium carbonate → tert-Butyl (2-bromo-5-formylpyridin-4-yl)carbamate

HRID 468886ノート

反応式

HRID 468886 の反応式
[Br:1][C:2]1[CH:9]=[C:8](I)[C:5]([CH:6]=[O:7])=[CH:4][N:3]=1.[C:11](=[O:18])([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])[NH2:12].C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.C(OCC)(=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[Br:1][C:2]1[CH:9]=[C:8]([NH:12][C:11](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15])[C:5]([CH:6]=[O:7])=[CH:4][N:3]=1

参加物

8

反応物 4

HCID 10796Cesium carbonateHCID 77922tert-Butyl carbamateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 574695636-Bromo-4-iodonicotinaldehyde

生成物 1

HCID 86674965tert-Butyl (2-bromo-5-formylpyridin-4-yl)carbamate収率 40%

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 8857Ethyl Acetate溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
90 °C

実験手順

A mixture of 6-bromo-4-iodonicotinaldehyde (50 mg, 0.2 mmol), tert-butyl carbamate (28 mg, 0.24 mmol), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (18 mg, 0.03 mmol), palladium acetate (5 mg, 0.02 mmol), and cesium carbonate (100 mg, 0.32 mmol) in 1,4-dioxane (1 mL) was heated at 90° C. for 1 hour. The cooled reaction mixture was diluted with ethyl acetate (50 mL) and washed with water (100 mL). The organic layer was separated, dried over sodium sulfate, filtered, and evaporated in vacuo to afford a residue that was purified by flash chromatography (silica, 4 g, ISCO, 0-50% ethyl acetate in heptane) to afford the title compound as a white solid (18 mg, 40%). 1H NMR (400 MHz, CDCl3) δ 10.42 (s, 1H), 9.93 (s, 1H), 8.61 (s, 1H), 8.50 (s, 1H), 1.55 (s, 9H).

後処理

  1. customThe cooled reaction mixture
  2. washwashed with water (100 mL)
  3. customThe organic layer was separated
  4. dry with materialdried over sodium sulfate
  5. filtrationfiltered
  6. customevaporated in vacuo
  7. customto afford a residue that
  8. customwas purified by flash chromatography (silica, 4 g, ISCO, 0-50% ethyl acetate in heptane)

出典と根拠

ORDレコード
ord-ed420e05303c4d6882c64a656cf89978
出典データセット
uspto-grants-2014_01
特許番号
US08623889B2

反応ノート

読み込み中…