Tributylvinyltin → Methyl 3-ethenylpyridine-2-carboxylate

HRID 388912ノート

反応式

HRID 388912 の反応式
FC(F)(F)S(O[C:7]1[C:8]([C:13]([O:15][CH3:16])=[O:14])=[N:9][CH:10]=[CH:11][CH:12]=1)(=O)=O.[Li+].[Cl-].[CH2:21]([Sn](CCCC)(CCCC)C=C)[CH2:22]CC>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>[CH:21]([C:7]1[C:8]([C:13]([O:15][CH3:16])=[O:14])=[N:9][CH:10]=[CH:11][CH:12]=1)=[CH2:22]

参加物

6

反応物 3

HCID 81998TributylvinyltinHCID 433294Lithium ChlorideHCID 11066008Methyl 3-(trifluoromethylsulfonyloxy)-pyridine-2-carboxylate

生成物 1

HCID 15257081Methyl 3-ethenylpyridine-2-carboxylate

試薬・触媒・溶媒 2

HCID 178418476HCID 178418476、化合物触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
100 °C

実験手順

To a solution of methyl 3-(trifluoromethylsulfonyloxy)picolinate (i.e., Cap-174, Step a) (570 mg, 2.0 mmol), an intermediate in the preparation of Cap-174, in DMF (20 mL) was added LiCl (254 mg, 6.0 mmol), tributyl(vinyl)stannane (761 mg, 2.4 mmol) and bis(triphenylphosphine)palladium dichloride (42 mg, 0.06 mmol). The mixture was heated at 100° C. for 4 h before the solvent was removed in vacuo. The residue was taken up in acetonitrile (50 mL) and hexanes (50 mL) and the resulting mixture was washed twice with hexanes. The acetonitrile layer was then separated, filtered through CELITE®, and evaporated. Purification of the residue by flash chromatography on a Horizon instrument (gradient elution with 25% ethyl acetate in hexanes to 65% ethyl acetate in hexanes) afforded methyl 3-vinylpicolinate (i.e., Cap-175, Step a) (130 mg, 40%) as a yellow oil. 1H NMR (300 MHz, CDCl3) δ ppm 8.60 (1H, dd, J=4.6, 1.7 Hz), 7.94 (1H, d, J=7.7 Hz), 7.33-7.51 (2H, m), 5.72 (1H, d, J=17.2 Hz), 5.47 (1H, d, J=11.0 Hz), 3.99 (3H, s). Rt=1.29 min (Cond.-MD1); LC-MS: Anal. Calcd. for [M+H]+ C9H10NO2: 164.07. found: 164.06.

後処理

  1. customwas removed in vacuo
  2. washhexanes (50 mL) and the resulting mixture was washed twice with hexanes
  3. customThe acetonitrile layer was then separated
  4. filtrationfiltered through CELITE®
  5. customevaporated
  6. customPurification of the residue by flash chromatography
  7. washon a Horizon instrument (gradient elution with 25% ethyl acetate in hexanes to 65% ethyl acetate in hexanes)

出典と根拠

ORDレコード
ord-7eab4345290149a0bd26fd02e682df01
出典データセット
uspto-grants-2013_02
特許番号
US08377980B2

反応ノート

読み込み中…