(Z)-1-Ethoxy-2-(tributylstannyl)ethene → HCID 67261221, compound

HRID 2368793Notes

Reaction equation

HRID 2368793 reaction equation
[F:1][C:2]1[CH:24]=[C:23]([F:25])[CH:22]=[CH:21][C:3]=1[CH2:4][C:5]1[CH:6]=[C:7](I)[C:8](=[O:19])[N:9]([CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=2[F:18])[CH:10]=1.[CH2:26]([O:28]C=C[Sn](CCCC)(CCCC)CCCC)[CH3:27]>CN(C=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[C:26]([C:7]1[C:8](=[O:19])[N:9]([CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=2[F:18])[CH:10]=[C:5]([CH2:4][C:3]2[CH:21]=[CH:22][C:23]([F:25])=[CH:24][C:2]=2[F:1])[CH:6]=1)(=[O:28])[CH3:27]

Participants

5

Reactant 2

HCID 2763294(Z)-1-Ethoxy-2-(tributylstannyl)etheneHCID 67261866HCID 67261866, compound

Product 1

HCID 67261221HCID 67261221, compound

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolvent

Procedure

A mixture of 5-(2,4-difluorobenzyl)-1-(2-fluorobenzyl)-3-iodopyridin-2(1H)-one 5 (6.61 g, 14.5 mmol), bis(triphenylphosphine)palladium(II) chloride (1.02 g, 1.5 mmol), and ethoxyvinyl(tributyl)tin (10.81 g, 29.0 mmol) in anhydrous DMF (145 ml) was heated at 700 under argon condition for 1 h. DMF was distilled off and the resulting residue was dissolved in ethyl acetate (145 ml) and filtered through a pad of celite. The filtrate was stirred with 1N HCl (145 ml) for 15 min, washed with water (2×145 ml), brine (145 ml), dried over anhydrous sodium sulfate, and distilled off. The residue was purified by flash column chromatography on silica gel (hexanes:ethyl acetate, 80:20). Yield 4.21 g (78%). 1H NMR (CDCl3, 500 MHz): δ 7.98 (d, 1H, J=2.6 Hz), 7.49-7.44 (m, 2H), 7.35-7.30 (m, 1H), 7.16-7.07 (m, 3H), 6.85-6.78 (m, 2H), 5.17 (s, 2H), 3.71 (s, 2H), 2.67 (s, 3H). 13C NMR (CDCl3, 125 MHz): δ 197.6, 162.4, 162.1, 160.5, 160.4, 160.2, 144.4, 141.4, 131.4, 131.2, 130.4, 127.7, 124.6, 122.6, 122.1, 116.9, 115.6, 111.5, 104.1, 47.2, 30.9, 30.5.

Workup

  1. temperaturewas heated at 700 under argon condition for 1 h
  2. distillationDMF was distilled off
  3. dissolutionthe resulting residue was dissolved in ethyl acetate (145 ml)
  4. filtrationfiltered through a pad of celite
  5. washwashed with water (2×145 ml), brine (145 ml)
  6. dry with materialdried over anhydrous sodium sulfate
  7. distillationdistilled off
  8. customThe residue was purified by flash column chromatography on silica gel (hexanes:ethyl acetate, 80:20)

Sources & evidence

ORD record
ord-c8b939737b464f168533e15570e88186
Source dataset
uspto-grants-2014_04
Patent number
US08703801B2

Reaction notes

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