Cesium carbonate → Tert-butyl 6-amino-3-(2-formylfuran-3-yl)-2-hydroxybenzoate

HRID 1778383ノート

反応式

HRID 1778383 の反応式
[NH2:1][C:2]1[C:7]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])=[C:6]([OH:15])[C:5](Br)=[CH:4][CH:3]=1.[CH:17]([C:19]1[O:20][CH:21]=[CH:22][C:23]=1B1OC(C)(C)C(C)(C)O1)=[O:18].F[B-](F)(F)F.C([PH+](C(C)(C)C)C(C)(C)C)(C)(C)C.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[NH2:1][C:2]1[C:7]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])=[C:6]([OH:15])[C:5]([C:23]2[CH:22]=[CH:21][O:20][C:19]=2[CH:17]=[O:18])=[CH:4][CH:3]=1

参加物

8

反応物 4

HCID 10796Cesium carbonateHCID 2734635Tri-tert-butylphosphine tetrafluoroborateHCID 164141993-(Tetramethyl-1,3,2-dioxaborolan-2-yl)furan-2-carbaldehydeHCID 66685946Tert-butyl 6-amino-3-bromo-2-hydroxybenzoate2 回

生成物 1

HCID 86684736Tert-butyl 6-amino-3-(2-formylfuran-3-yl)-2-hydroxybenzoate収率 69.9%

試薬・触媒・溶媒 3

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 962Water溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
70 °C

実験手順

A mixture of tert-butyl 6-amino-3-bromo-2-hydroxybenzoate (Intermediate 62, 1.16 g), 2-formylfuran-3-boronic acid pinacol ester (1.073 g), tris-(dibenzylideneacetone)dipalladium (0.184 g), tri-tert-butylphosphonium tetrafluoroborate (0.117 g) and cesium carbonate (3.935 g) was suspended in dioxane (40 mL) and water (5 mL). The mixture was de-gassed and flushed with nitrogen then heated at 70° C. for 3 hours. After cooling, the mixture was concentrated in vacuo. The residue was partitioned between water and ethyl acetate and the combined organic layers were dried (MgSO4) and filtered. The filtrate was concentrated in vacuo and the residue was purified by chromatography on silica, eluting with a mixture of ethyl acetate and cyclohexane, with a gradient of 2.5-25% to give tert-butyl 6-amino-3-(2-formylfuran-3-yl)-2-hydroxybenzoate (0.854 g) as a yellow oil.

後処理

  1. customThe mixture was de-gassed
  2. customflushed with nitrogen
  3. temperatureAfter cooling
  4. concentrationthe mixture was concentrated in vacuo
  5. customThe residue was partitioned between water and ethyl acetate
  6. dry with materialthe combined organic layers were dried (MgSO4)
  7. filtrationfiltered
  8. concentrationThe filtrate was concentrated in vacuo
  9. customthe residue was purified by chromatography on silica
  10. washeluting with a mixture of ethyl acetate and cyclohexane, with a gradient of 2.5-25%

出典と根拠

ORDレコード
ord-9060a67989b84c98844290231f824fb5
出典データセット
uspto-grants-2016_02
特許番号
US09266896B2

反応ノート

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