Acetone → methyl 2-[(3R,4R)-3-(1-benzyloxycarbonyloxy-1-methylethyl)-3-isocyano-2-oxo-4-allylazetidin-1-yl]-3-methylbut-2-enoate

HRID 1719322ノート

反応式

HRID 1719322 の反応式
[N+:1]([C@@H:3]1[C@@H:6]([CH2:7][CH:8]=[CH2:9])[N:5]([C:10](=[C:15]([CH3:17])[CH3:16])[C:11]([O:13][CH3:14])=[O:12])[C:4]1=[O:18])#[C-:2].C([Li])CCC.[CH3:24][C:25]([CH3:27])=[O:26].Cl[C:29]([O:31][CH2:32][C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)=[O:30]>O1CCCC1.C(O)(=O)C>[CH2:32]([O:31][C:29]([O:26][C:25]([C@:3]1([N+:1]#[C-:2])[C@@H:6]([CH2:7][CH:8]=[CH2:9])[N:5]([C:10](=[C:15]([CH3:17])[CH3:16])[C:11]([O:13][CH3:14])=[O:12])[C:4]1=[O:18])([CH3:27])[CH3:24])=[O:30])[C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1

参加物

7

反応物 4

HCID 180AcetoneHCID 10387Benzyl chloroformateHCID 54071546methyl 2-[(3R,4R)-3-isocyano-2-oxo-4-allylazetidin-1-yl]-3-methylbut-2-enoateHCID 178418339Butyllithium

生成物 1

HCID 18599215methyl 2-[(3R,4R)-3-(1-benzyloxycarbonyloxy-1-methylethyl)-3-isocyano-2-oxo-4-allylazetidin-1-yl]-3-methylbut-2-enoate

試薬・触媒・溶媒 2

HCID 176Acetic Acid溶媒HCID 8028Tetrahydrofuran溶媒3 回

反応条件

温度
-78 °C

実験手順

To a solution of methyl 2-[(3R,4R)-3-isocyano-2-oxo-4-allylazetidin-1-yl]-3-methylbut-2-enoate (198.0 mg) in tetrahydrofuran (3.96 ml) was added dropwise a solution of n-butyl lithium (0.634 ml of 1.51M solution in hexane) at -78° C. over a period of 5 minutes. After stirring for 15 minutes at -78° C., the reaction mixture was added with a solution of acetone (0.0713 ml) in tetrahydrofuran (0.642 ml) at -78° C. over a period of 5 minutes. After stirring for 25 minutes at -78° C., the reaction mixture was added dropwise with a solution of benzyl chloroformate (0.1274 ml) in tetrahydrofuran (1.15 ml) at -78° C. over a period of 5 minutes. The resulting solution was allowed to warm to 0° C. over a period of 40 minutes and added with acetic acid (0.0639 ml) at 0° C. The solvent was distilled off in vacuo at 0° C. and the residue was dissolved in ethyl acetate (30 ml) and washed with brine, aqueous sodium bicarbonate, brine, and saturated aqueous sodium chloride. After drying over magnesium sulfate, the ethyl acetate extract was filtered and evaporated in vacuo. The residual oil (381.2 mg) was chromatographed on silica gel (11 g) eluting with a mixture of ethyl acetate and hexane (1:10→1:5) to give methyl 2-[(3R,4R)-3-(1-benzyloxycarbonyloxy-1-methylethyl)-3-isocyano-2-oxo-4-allylazetidin-1-yl]-3-methylbut-2-enoate (221.2 mg) as an oil.

後処理

  1. stirringAfter stirring for 25 minutes at -78° C.
  2. temperatureto warm to 0° C. over a period of 40 minutes
  3. distillationThe solvent was distilled off in vacuo at 0° C.
  4. dissolutionthe residue was dissolved in ethyl acetate (30 ml)
  5. washwashed with brine, aqueous sodium bicarbonate, brine, and saturated aqueous sodium chloride
  6. dry with materialAfter drying over magnesium sulfate
  7. extractionthe ethyl acetate extract
  8. filtrationwas filtered
  9. customevaporated in vacuo
  10. customThe residual oil (381.2 mg) was chromatographed on silica gel (11 g)
  11. washeluting with a mixture of ethyl acetate and hexane (1:10→1:5)

出典と根拠

ORDレコード
ord-782f6cef43fc4f82aec00bdb695e9a69
出典データセット
uspto-grants-1985_09
特許番号
US04539152

反応ノート

読み込み中…