3-Methyl-2-butenyl tert-butyl diazomalonate | 128541-14-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 3-Methyl-2-butenyl tert-butyl diazomalonate
• 英文别名: 3-O-tert-butyl 1-O-(3-methylbut-2-enyl) 2-diazopropanedioate
• CAS: 128541-14-0
• 化学式: C₁₂H₁₈N₂O₄
• 分子量: 254.286
• InChiKey: RXRYUNVKCYDIFI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  54.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3-Methyl-2-butenyl tert-butyl diazomalonate 在 triethylphosphite copper(I) iodide complex 盐酸 、 sodium hydroxide 、 二苯基膦叠氮化物 、 三乙胺 、 三氟乙酸 作用下， 以 1,4-二氧六环 、 二氯甲烷 、 甲苯 为溶剂， 反应 5.0h， 生成 (E)-1-Amino-2-(hydroxymethyl)-3,3-dimethylcyclopropane-1-carboxylic acid
  参考文献：
  名称：

  Intramolecular cyclopropanation: stereospecific synthesis of (E)- and (Z)-1-aminocyclopropane-1-carboxylic acids

  摘要：

  tert-Butyl-substituted allyl malonates, prepared in two steps from malonic acid, are diazotized in high yields. The diazomalonates 7 undergo a stereospecific copper(I)-catalyzed cyclopropanation to give 1-(tert-butoxycarbonyl)-3-oxa-2-oxobicyclo[3.1.0]hexanes 8 which can be converted to the protected (E)- or (Z)-1-aminocyclopropane-1-carboxylic acids 10 or 15 via Curtius- or Hoffmann-type rearrangements, respectively. The sequences are short (six steps from malonic acid) and proceed with good overall yields (20-40% overall from malonic acid) The free amino acids 12 and 18 can be liberated in two steps.

  DOI：

  10.1021/jo00056a020
• 作为产物：
  描述：

  丙二酸单叔丁酯 在 4-二甲氨基吡啶 、 对甲苯磺酰叠氮 、 potassium carbonate 、 N,N'-二环己基碳二亚胺 作用下， 以 乙腈 为溶剂， 生成 3-Methyl-2-butenyl tert-butyl diazomalonate
  参考文献：
  名称：

  Intramolecular cyclopropanation: stereospecific synthesis of (E)- and (Z)-1-aminocyclopropane-1-carboxylic acids

  摘要：

  tert-Butyl-substituted allyl malonates, prepared in two steps from malonic acid, are diazotized in high yields. The diazomalonates 7 undergo a stereospecific copper(I)-catalyzed cyclopropanation to give 1-(tert-butoxycarbonyl)-3-oxa-2-oxobicyclo[3.1.0]hexanes 8 which can be converted to the protected (E)- or (Z)-1-aminocyclopropane-1-carboxylic acids 10 or 15 via Curtius- or Hoffmann-type rearrangements, respectively. The sequences are short (six steps from malonic acid) and proceed with good overall yields (20-40% overall from malonic acid) The free amino acids 12 and 18 can be liberated in two steps.

  DOI：

  10.1021/jo00056a020

文献信息

• Diazo transfer reactions under mildly basic conditions
  作者：Ari M. P. Koskinen、Luis Muñoz

  DOI：10.1039/c39900000652

  日期：——

  Practically quantitative diazo transfer from toluene-p-sulphonyl azide to active methylene compounds has been achieved rapidly under mildly basic conditions with potassium carbonate in acetonitrile.

  在碳酸钾的乙腈溶液中，在温和的碱性条件下，已迅速实现了重氮从甲苯-对-磺酰叠氮化物到活性亚甲基化合物的定量转移。
• KOSKINEN, ARI M. P.;MUNOZ, LUIS, J. CHEM. SOC. CHEM. COMMUN.,(1990) N, C. 652-653
  作者：KOSKINEN, ARI M. P.、MUNOZ, LUIS

  DOI：——

  日期：——
• Intramolecular cyclopropanation: stereospecific synthesis of (E)- and (Z)-1-aminocyclopropane-1-carboxylic acids
  作者：Ari M. P. Koskinen、Luis Munoz

  DOI：10.1021/jo00056a020

  日期：1993.2

  tert-Butyl-substituted allyl malonates, prepared in two steps from malonic acid, are diazotized in high yields. The diazomalonates 7 undergo a stereospecific copper(I)-catalyzed cyclopropanation to give 1-(tert-butoxycarbonyl)-3-oxa-2-oxobicyclo[3.1.0]hexanes 8 which can be converted to the protected (E)- or (Z)-1-aminocyclopropane-1-carboxylic acids 10 or 15 via Curtius- or Hoffmann-type rearrangements, respectively. The sequences are short (six steps from malonic acid) and proceed with good overall yields (20-40% overall from malonic acid) The free amino acids 12 and 18 can be liberated in two steps.