Acetic Acid → methyl 2-{(3S,4R)-3-[1-methyl-1-(4-nitrobenzyloxycarbonyloxy)ethyl]-2-oxo-4-allylazetidin-1-yl}-3-methylbut-2-enoate

HRID 851402ノート

反応式

HRID 851402 の反応式
C([Li])CCC.[OH:6][C:7]([C@@H:10]1[C@@H:13]([CH2:14][CH:15]=[CH2:16])[N:12]([C:17](=[C:22]([CH3:24])[CH3:23])[C:18]([O:20][CH3:21])=[O:19])[C:11]1=[O:25])([CH3:9])[CH3:8].Cl[C:27]([O:29][CH2:30][C:31]1[CH:36]=[CH:35][C:34]([N+:37]([O-:39])=[O:38])=[CH:33][CH:32]=1)=[O:28].C(O)(=O)C>O1CCCC1>[CH3:23][C:22]([CH3:24])=[C:17]([N:12]1[C@H:13]([CH2:14][CH:15]=[CH2:16])[C@@H:10]([C:7]([CH3:9])([O:6][C:27]([O:29][CH2:30][C:31]2[CH:32]=[CH:33][C:34]([N+:37]([O-:39])=[O:38])=[CH:35][CH:36]=2)=[O:28])[CH3:8])[C:11]1=[O:25])[C:18]([O:20][CH3:21])=[O:19]

参加物

6

反応物 4

HCID 176Acetic AcidHCID 782054-Nitrobenzyl chloroformateHCID 22823199methyl 2-[(3S,4R)-3-(1-hydroxy-1-methylethyl)-2-oxo-4-allylazetidin-1-yl]-3-methylbut-2-enoateHCID 178418339Butyllithium

生成物 1

HCID 56623914methyl 2-{(3S,4R)-3-[1-methyl-1-(4-nitrobenzyloxycarbonyloxy)ethyl]-2-oxo-4-allylazetidin-1-yl}-3-methylbut-2-enoate収率 55%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-70 °C

実験手順

A solution of n-butyl lithium (0.42 ml of 1.55 M solution in hexane) was added to a solution of methyl 2-[(3S,4R)-3-(1-hydroxy-1-methylethyl)-2-oxo-4-allylazetidin-1-yl]-3-methylbut-2-enoate (150 mg) in tetrahydrofuran (3 ml) during 3 minutes at -70° C. and the mixture was stirred for 5 minutes at -70° C. A solution of p-nitrobenzyl chloroformate (161 mg) in tetrahydrofuran (1.6 ml) was added to the mixture during 5 minutes at -70° C. and the mixture was stirred for 15 minutes at -70° C. The mixture was allowed to warm to 0° C. during 30 minutes and stirred for 2 hours at 0° C. Acetic acid (0.037 ml) was added to the mixture at 0° C. and the mixture was evaporated in vacuo. The residue was dissolved in ethyl acetate (50 ml), and the sodium was washed with water (10 ml), 10% phosphoric acid (10 ml), phosphate buffer (pH 7.0) (10 ml×2), aqueous sodium bicarbonate and brine. The organic layer was dried over magnesium sulfate and evaporated in vacuo. The residue was chromatographed on silica gel (10 g) eluting with a mixture of hexane and ethyl acetate (5:1-1:1) to give methyl 3-methyl-2-[(3S,4R)-3-[1-methyl-1-(4-nitrobenzyloxycarbonyloxy)ethyl]-2-oxo-4-allylazetidin-1-yl]but-2-enoate (135 mg) as an oil.

後処理

  1. stirringthe mixture was stirred for 15 minutes at -70° C
  2. temperatureto warm to 0° C. during 30 minutes
  3. stirringstirred for 2 hours at 0° C
  4. customthe mixture was evaporated in vacuo
  5. dissolutionThe residue was dissolved in ethyl acetate (50 ml)
  6. washthe sodium was washed with water (10 ml), 10% phosphoric acid (10 ml), phosphate buffer (pH 7.0) (10 ml×2), aqueous sodium bicarbonate and brine
  7. dry with materialThe organic layer was dried over magnesium sulfate
  8. customevaporated in vacuo
  9. customThe residue was chromatographed on silica gel (10 g)
  10. washeluting with a mixture of hexane and ethyl acetate (5:1-1:1)

出典と根拠

ORDレコード
ord-15297d9720544e16b0ddeebf661c5369
出典データセット
uspto-grants-1983_05
特許番号
US04383945

反応ノート

読み込み中…