(Z)-3-(Tributylstannyl)prop-2-en-1-ol → methyl 7-{N-[4-fluoro-2-((Z)-3-hydroxy-prop-1-enyl)-benzenesulfonyl]-N-(methoxycarbonyl)amino}-4H-furo[2,3-c]chromene-6-carboxylate

HRID 1778406ノート

反応式

HRID 1778406 の反応式
Br[C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[S:9]([N:12]([C:17]1[C:26]([C:27]([O:29][CH3:30])=[O:28])=[C:25]2[C:20]([C:21]3[CH:33]=[CH:32][O:31][C:22]=3[CH2:23][O:24]2)=[CH:19][CH:18]=1)[C:13]([O:15][CH3:16])=[O:14])(=[O:11])=[O:10].C([Sn](CCCC)(CCCC)/[CH:39]=[CH:40]\[CH2:41][OH:42])CCC>O1CCOCC1.O>[F:8][C:6]1[CH:5]=[CH:4][C:3]([S:9]([N:12]([C:17]2[C:26]([C:27]([O:29][CH3:30])=[O:28])=[C:25]3[C:20]([C:21]4[CH:33]=[CH:32][O:31][C:22]=4[CH2:23][O:24]3)=[CH:19][CH:18]=2)[C:13]([O:15][CH3:16])=[O:14])(=[O:11])=[O:10])=[C:2](/[CH:39]=[CH:40]\[CH2:41][OH:42])[CH:7]=1

参加物

5

反応物 2

HCID 9974944(Z)-3-(Tributylstannyl)prop-2-en-1-ol2 回HCID 66685495methyl 7-{N-[2-bromo-4-fluorobenzenesulfonyl]-N-(methoxycarbonyl)amino}-4H-furo[2,3-c]chromene-6-carboxylate2 回

生成物 1

HCID 68093356methyl 7-{N-[4-fluoro-2-((Z)-3-hydroxy-prop-1-enyl)-benzenesulfonyl]-N-(methoxycarbonyl)amino}-4H-furo[2,3-c]chromene-6-carboxylate収率 78.3%

試薬・触媒・溶媒 2

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 methyl 7-{N-[2-bromo-4-fluorobenzenesulfonyl]-N-(methoxycarbonyl)amino}-4H-furo[2,3-c]chromene-6-carboxylate (Intermediate 93, 0.200 g) and (Z)-3-tributylstannanyl-prop-2-en-1-ol (Intermediate 1, 0.230 g) in dioxane (9 mL) and water (1 mL) was de-gassed and flushed with nitrogen. tris-(Dibenzylideneacetone)dipalladium (0.034 g) and tri-tert-butylphosphonium tetrafluoroborate (0.022 g) were added and the reaction mixture was heated to 70° C. for 30 minutes. The mixture was diluted with ethyl acetate and filtered. The filtrate was washed with water, dried (MgSO4) and filtered. The filtrate was concentrated in vacuo and the residue was purified by chromatography on silica, pre-equilibrated with ammonia solution in DCM, eluting with a mixture of ethyl acetate and cyclohexane, with a gradient of 0-100%. The resultant product was triturated with ether to give methyl 7-{N-[4-fluoro-2((Z)-3-hydroxyprop-1-enyl)benzenesulfonyl]-N-(methoxycarbonyl)amino}-4H-furo[2,3-c]chromene-6-carboxylate (0.150 g) as a cream powder.

後処理

  1. customwas de-gassed
  2. customflushed with nitrogen
  3. additiontris-(Dibenzylideneacetone)dipalladium (0.034 g) and tri-tert-butylphosphonium tetrafluoroborate (0.022 g) were added
  4. additionThe mixture was diluted with ethyl acetate
  5. filtrationfiltered
  6. washThe filtrate was washed with water
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationThe filtrate was concentrated in vacuo
  10. customthe residue was purified by chromatography on silica, pre-equilibrated with ammonia solution in DCM
  11. washeluting with a mixture of ethyl acetate and cyclohexane, with a gradient of 0-100%
  12. customThe resultant product was triturated with ether

出典と根拠

ORDレコード
ord-294bd64bb29d40bcba5de9c25b8383f5
出典データセット
uspto-grants-2016_02
特許番号
US09266896B2

反応ノート

読み込み中…