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

HRID 1778383노트

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HRID 1778383 반응식
[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

참가 물질

8

반응물 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-hydroxybenzoate2회

생성물 1

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

시약·촉매·용매 3

HCID 9811564Bis(dibenzylideneacetone)palladium촉매HCID 962Water용매HCID 312751,4-Dioxane용매

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온도
70 °C

실험 절차

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.

후처리

  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%

출처 및 근거

ORD 기록
ord-9060a67989b84c98844290231f824fb5
출처 데이터셋
uspto-grants-2016_02
특허 번호
US09266896B2

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