Pivalaldehyde → Methyl (Z)-2-[(tert-butoxycarbonyl)amino]-4,4-dimethylpent-2-enoate

HRID 658134ノート

反応式

HRID 658134 の反応式
[CH:1](=O)[C:2]([CH3:5])([CH3:4])[CH3:3].[C:7]([O:11][C:12]([NH:14][CH:15](P(OC)(OC)=O)[C:16]([O:18][CH3:19])=[O:17])=[O:13])([CH3:10])([CH3:9])[CH3:8]>C1COCC1>[C:7]([O:11][C:12]([NH:14]/[C:15](=[CH:1]\[C:2]([CH3:5])([CH3:4])[CH3:3])/[C:16]([O:18][CH3:19])=[O:17])=[O:13])([CH3:10])([CH3:9])[CH3:8]

参加物

4

反応物 2

HCID 12417PivalaldehydeHCID 397380Methyl ((tert-butoxy(hydroxy)methylidene)amino)(dimethoxyphosphoryl)acetate

生成物 1

HCID 59302433Methyl (Z)-2-[(tert-butoxycarbonyl)amino]-4,4-dimethylpent-2-enoate

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-70 °C

実験手順

Pivalaldehyde (303.2 g, 3.41 mol, 10 eq.) and methyl {[(tert-butoxy)carbonyl]amino}-(dimethoxyphosphoryl)acetate (101.5 g, 0.341 mol, 1.0 eq.) are dissolved in THF (800 ml) and cooled to −70° C. At −70° C., TMG (78.7 g, 0.683 mmol, 6.95 ml, 2.0 eq.) is slowly added dropwise and the mixture is then stirred at −70° C. for 4 h and subsequently at RT for 4 days. The reaction mixture is concentrated and then extracted by shaking with ethyl acetate (twice 500 ml) and water, and the combined org. phases are washed with a sat. sodium chloride solution (100 ml) and dried over sodium sulfate. After concentration the crude product is chromatographed (1.5 kg of silica gel, eluent: cyclohexane/ethyl acetate 5:1). 67 g (76% of theory) of the title compound are obtained.

後処理

  1. additionAt −70° C., TMG (78.7 g, 0.683 mmol, 6.95 ml, 2.0 eq.) is slowly added dropwise
  2. concentrationThe reaction mixture is concentrated
  3. extractionextracted
  4. stirringby shaking with ethyl acetate (twice 500 ml) and water
  5. washphases are washed with a sat. sodium chloride solution (100 ml)
  6. dry with materialdried over sodium sulfate
  7. concentrationAfter concentration the crude product
  8. customis chromatographed (1.5 kg of silica gel, eluent: cyclohexane/ethyl acetate 5:1)

出典と根拠

ORDレコード
ord-aae22c08ce45473791dac7f143857499
出典データセット
uspto-grants-2011_12
特許番号
US08076285B2

反応ノート

読み込み中…