Potassium Fluoride → ethyl (2E,4E)-5-(8-hydroxy-2,3,7,9,9-pentamethyl-1,4-dioxaspiro[4.5]dec-6-en-8-yl)-3-(trifluoromethyl)penta-2,4-dienoate

HRID 713620ノート

反応式

HRID 713620 の反応式
[CH3:1][CH:2]1[CH:6]([CH3:7])[O:5][C:4]2([CH2:12][C:11]([CH3:14])([CH3:13])[C:10](/[CH:16]=[CH:17]/[Sn](CCCC)(CCCC)CCCC)([OH:15])[C:9]([CH3:31])=[CH:8]2)[O:3]1.[F:32][C:33]([F:43])([F:42])/[C:34](/I)=[CH:35]/[C:36]([O:38][CH2:39][CH3:40])=[O:37].[F-].[K+]>CC#N.CC#N.Cl[Pd]Cl.CN(C)C=O>[OH:15][C:10]1(/[CH:16]=[CH:17]/[C:34](/[C:33]([F:32])([F:42])[F:43])=[CH:35]\[C:36]([O:38][CH2:39][CH3:40])=[O:37])[C:11]([CH3:14])([CH3:13])[CH2:12][C:4]2([O:5][CH:6]([CH3:7])[CH:2]([CH3:1])[O:3]2)[CH:8]=[C:9]1[CH3:31]

参加物

6

反応物 3

HCID 522689Potassium FluorideHCID 10870101ethyl (2Z)-4,4,4-trifluoro-3-iodobut-2-enoateHCID 708734232,3,7,9,9-Pentamethyl-8-[(E)-2-(tributylstannyl)vinyl]-1,4-dioxaspiro[4.5]dec-6-en-8-ol

生成物 1

HCID 86713142ethyl (2E,4E)-5-(8-hydroxy-2,3,7,9,9-pentamethyl-1,4-dioxaspiro[4.5]dec-6-en-8-yl)-3-(trifluoromethyl)penta-2,4-dienoate収率 65.2%

試薬・触媒・溶媒 2

HCID 6093782Bis(acetonitrile)dichloropalladium触媒HCID 6228Dimethylformamide溶媒

実験手順

Under argon, 2,3,7,9,9-pentamethyl-8-[(E)-2-(tributylstannyl)vinyl]-1,4-dioxaspiro[4.5]dec-6-en-8-ol (300 mg, 0.55 mmol) and ethyl (2Z)-4,4,4-trifluoro-3-iodobut-2-enoate (163 mg, 0.55 mmol) in a round-bottom flask that had been dried by heating were dissolved in abs. N,N-dimethylformamide (4 ml), dichlorobis(acetonitrile)palladium(II) (7 mg, 0.03 mmol) was added and the mixture was stirred at room temperature for 3 h. After the addition of potassium fluoride solution, the reaction mixture was stirred further at room temperature overnight. The aqueous phase was then repeatedly extracted thoroughly with diethyl ether, and the combined organic phases were then dried over magnesium sulfate, filtered and concentrated under reduced pressure. By final column chromatography purification of the resulting crude product (ethyl acetate/heptane gradient), ethyl (2E,4E)-5-(8-hydroxy-2,3,7,9,9-pentamethyl-1,4-dioxaspiro[4.5]dec-6-en-8-yl)-3-(trifluoromethyl)penta-2,4-dienoate (150 mg, 61% of theory) was obtained in the form of a colorless oil. 1H-NMR (400 MHz, CDCl3 δ, ppm) 7.47 (d, 1H), 6.29 (d, 1H), 6.25 (s, 1H), 5.48 (s, 1H), 4.26 (q, 2H), 3.68 (m, 1H), 3.59 (m, 1H), 1.93 (d, 1H), 1.83 (br. m, 1H, OH), 1.77 (d, 1H), 1.69 (s, 3H), 1.32 (t, 3H), 1.25 (m, 3H), 1.18 (m, 3H), 1.10 (s, 3H), 0.91 (s, 3H).

後処理

  1. temperatureby heating
  2. dissolutionwere dissolved in abs
  3. stirringthe reaction mixture was stirred further at room temperature overnight
  4. extractionThe aqueous phase was then repeatedly extracted thoroughly with diethyl ether
  5. dry with materialthe combined organic phases were then dried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customBy final column chromatography purification of the resulting crude product (ethyl acetate/heptane gradient)

出典と根拠

ORDレコード
ord-6cfdf53ef1e54c4e80476a2b4e24f3e3
出典データセット
uspto-grants-2015_11
特許番号
US09185914B2

反応ノート

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