Lithium Chloride → Tert-butyl 2-[3-(2,2-dimethylpropionylamino)-2-methoxycarbonylphenylethynyl]-pyrrolidine-1-carboxylate

HRID 715972

反応式

HRID 715972 の反応式
[CH3:1][C:2]([CH3:25])([CH3:24])[C:3]([NH:5][C:6]1[CH:15]=[CH:14][CH:13]=[C:12](OS(C(F)(F)F)(=O)=O)[C:7]=1[C:8]([O:10][CH3:11])=[O:9])=[O:4].C([Sn](CCCC)(CCCC)[C:31]#[C:32][CH:33]1[CH2:37][CH2:36][CH2:35][N:34]1[C:38]([O:40][C:41]([CH3:44])([CH3:43])[CH3:42])=[O:39])CCC.[Cl-].[Li+]>CN(C)C=O.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>[CH3:1][C:2]([CH3:25])([CH3:24])[C:3]([NH:5][C:6]1[C:7]([C:8]([O:10][CH3:11])=[O:9])=[C:12]([C:31]#[C:32][CH:33]2[CH2:37][CH2:36][CH2:35][N:34]2[C:38]([O:40][C:41]([CH3:44])([CH3:43])[CH3:42])=[O:39])[CH:13]=[CH:14][CH:15]=1)=[O:4]

参加物

6

反応物 3

HCID 433294Lithium ChlorideHCID 70984584Tert-butyl 2-tributylstannanylethynylpyrrolidine-1-carboxylate2 回HCID 86712118Methyl 2-(2,2-dimethylpropionylamino)-6-trifluoromethanesulfonyloxybenzoate2 回

生成物 1

HCID 70982938Tert-butyl 2-[3-(2,2-dimethylpropionylamino)-2-methoxycarbonylphenylethynyl]-pyrrolidine-1-carboxylate収率 86.7%

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
95 °C

実験手順

A mixture of methyl 2-(2,2-dimethylpropionylamino)-6-trifluoromethanesulfonyloxybenzoate (Intermediate 39, 3.83 g), tert-butyl 2-tributylstannanylethynyl-pyrrolidine-1-carboxylate (Intermediate 41, 5.81 g), bis(triphenylphosphine)palladium(II) dichloride (0.702 g) and lithium chloride (1.28 g) in dimethylformamide (50 mL) was stirred and heated at 95° C. under nitrogen for 1 hour. After cooling, the mixture was concentrated in vacuo and the residue was partitioned between ethyl acetate and water. The organic layer was washed with water, dried (Na2SO4) 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 0-25% to give tert-butyl 2-[3-(2,2-dimethylpropionylamino)-2-methoxycarbonyl-phenylethynyl]-pyrrolidine-1-carboxylate (3.71 g) as a viscous gum.

後処理

  1. temperatureAfter cooling
  2. concentrationthe mixture was concentrated in vacuo
  3. customthe residue was partitioned between ethyl acetate and water
  4. washThe organic layer was washed with water
  5. dry with materialdried (Na2SO4)
  6. filtrationfiltered
  7. concentrationThe filtrate was concentrated in vacuo
  8. customthe residue was purified by chromatography on silica
  9. washeluting with a mixture of ethyl acetate and cyclohexane with a gradient of 0-25%

出典と根拠

ORDレコード
ord-a95fe76c005a4de5852ca2e20558e15c
出典データセット
uspto-grants-2015_11
特許番号
US09187494B2

関連ノート

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