Cesium carbonate → 1,1-Dimethylethyl (6-formyl-3-pyridinyl)methylcarbamate

HRID 906377ノート

反応式

HRID 906377 の反応式
Br[C:2]1[CH:3]=[CH:4][C:5]([CH:8]=[O:9])=[N:6][CH:7]=1.[CH3:10][NH:11][C:12](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.[Pd].[Pd].C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1>[CH:8]([C:5]1[N:6]=[CH:7][C:2]([CH2:10][NH:11][C:12](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[CH:3][CH:4]=1)=[O:9]

参加物

7

反応物 4

HCID 10796Cesium carbonateHCID 527635tert-Butyl methylcarbamateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 98775625-Bromopyridine-2-carbaldehyde

生成物 1

HCID 866181111,1-Dimethylethyl (6-formyl-3-pyridinyl)methylcarbamate収率 51.3%

試薬・触媒・溶媒 2

HCID 9832798Tris(dibenzylideneacetone) dipalladium触媒HCID 312751,4-Dioxane溶媒

反応条件

温度
110 °C

実験手順

A mixture of 5-bromo-2-pyridinecarbaldehyde (1.5 g, 8.064 mmol), 1,1-dimethylethyl methylcarbamate (D58) (1.267 g, 9.677 mmol), tris(dibenzylideneacetone) dipalladium(0) (0.148 g, 0.161 mmol), xantphos (0.373 g, 0.645 mmol) and cesium carbonate (3.678 g, 11.289 mmol) in dioxane (35 mL) was heated at 110° C. overnight under an argon atmosphere. On cooling, the solvent was removed in vacuo and the residue partitioned between EtOAc and water. The organic layer was separated, washed with water and brine, dried and concentrated to give the crude product which was purified by column chromatography. Elution with 0-50% ether/petroleum ether gave the title compound as a brown oil (0.977 g). δH (CDCl3, 400 MHz) 10.01 (1H, s), 8.79 (1H, d), 7.94 (1H, d), 7.86 (1H, dd), 3.40 (3H, s), 1.53 (9H, s). MS (ES): 259.1 (MNa+), 181.2, no molecular ion (MH+) observed.

後処理

  1. temperatureOn cooling
  2. customthe solvent was removed in vacuo
  3. customthe residue partitioned between EtOAc and water
  4. customThe organic layer was separated
  5. washwashed with water and brine
  6. customdried
  7. concentrationconcentrated
  8. customto give the crude product which
  9. customwas purified by column chromatography
  10. washElution with 0-50% ether/petroleum ether

出典と根拠

ORDレコード
ord-d0dd5d2d61794ca6bac2941f2fffab26
出典データセット
uspto-grants-2011_09
特許番号
US08012981B2

反応ノート

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