2-diazo-N-(3-methylhept-6-enoyl)-N-<2-(toluene-4-sulfonyl)ethyl>malonamic acid ethyl ester | 220445-77-2

• 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: 2-diazo-N-(3-methylhept-6-enoyl)-N-<2-(toluene-4-sulfonyl)ethyl>malonamic acid ethyl ester
• 英文别名: Ethyl 2-diazo-3-[3-methylhept-6-enoyl-[2-(4-methylphenyl)sulfonylethyl]amino]-3-oxopropanoate；ethyl 2-diazo-3-[3-methylhept-6-enoyl-[2-(4-methylphenyl)sulfonylethyl]amino]-3-oxopropanoate
• CAS: 220445-77-2
• 化学式: C₂₂H₂₉N₃O₆S
• 分子量: 463.555
• InChiKey: GEKZBRRXSMCJOI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  32
• 可旋转键数：
  13
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  108
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2-diazo-N-(3-methylhept-6-enoyl)-N-<2-(toluene-4-sulfonyl)ethyl>malonamic acid ethyl ester 在 dirhodium(II) tetrakis(perfluorobutyrate) 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以85%的产率得到3-methyl-9-oxo-10-<2-(toluene-4-sulfonyl)ethyl>-11-oxa-10-azatricyclo<6.2.1.0^1,6>undecane-8-carboxylic acid ethyl ester
  参考文献：
  名称：

  Generation and Trapping of N-Acyliminium Ions Derived from Isomünchnone Cycloadducts. A Versatile Route to Functionalized Heterocycles

  摘要：

  A series of 2-diazo-N-hept-6-enoylmalonamides were prepared and treated with a catalytic amount of rhodium(II) perfluorobutyrate. The resultant carbenoids underwent facile cyclization onto the neighboring amide carbonyl oxygen atom to generate isomunchnone-type intermediates. Subsequent 1,3-dipolar cycloaddition across the pendant olefin afforded intramolecular cycloadducts in high yield. The cascade sequence is simple, direct, and extremely tolerant of structural diversity. Exposure of these cycloadducts to Lewis acids resulted in oxabicyclic ring opening. N-Acyliminium ions of wide structural variety can be easily generated by this sequence of reactions. Different cyclization pathways become available depending on the nature of the substituent group attached to the amide nitrogen. When the tethered group is electrophilic in nature, proton lass from the initially formed N-acyliminium ion occurs rapidly to-give an acyl enamide which undergoes a subsequent cyclization at the electrophilic center.

  DOI：

  10.1021/jo981624e
• 作为产物：
  描述：

  2-[(4-甲基苯基)磺酰基]乙胺 在 三乙胺 、 甲烷磺酰基叠氮化物 、 N,N'-羰基二咪唑 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 18.0h， 生成 2-diazo-N-(3-methylhept-6-enoyl)-N-<2-(toluene-4-sulfonyl)ethyl>malonamic acid ethyl ester
  参考文献：
  名称：

  Generation and Trapping of N-Acyliminium Ions Derived from Isomünchnone Cycloadducts. A Versatile Route to Functionalized Heterocycles

  摘要：

  A series of 2-diazo-N-hept-6-enoylmalonamides were prepared and treated with a catalytic amount of rhodium(II) perfluorobutyrate. The resultant carbenoids underwent facile cyclization onto the neighboring amide carbonyl oxygen atom to generate isomunchnone-type intermediates. Subsequent 1,3-dipolar cycloaddition across the pendant olefin afforded intramolecular cycloadducts in high yield. The cascade sequence is simple, direct, and extremely tolerant of structural diversity. Exposure of these cycloadducts to Lewis acids resulted in oxabicyclic ring opening. N-Acyliminium ions of wide structural variety can be easily generated by this sequence of reactions. Different cyclization pathways become available depending on the nature of the substituent group attached to the amide nitrogen. When the tethered group is electrophilic in nature, proton lass from the initially formed N-acyliminium ion occurs rapidly to-give an acyl enamide which undergoes a subsequent cyclization at the electrophilic center.

  DOI：

  10.1021/jo981624e

文献信息

• Generation and Trapping of <i>N</i>-Acyliminium Ions Derived from Isomünchnone Cycloadducts. A Versatile Route to Functionalized Heterocycles
  作者：Michael A. Brodney、Albert Padwa

  DOI：10.1021/jo981624e

  日期：1999.1.1

  A series of 2-diazo-N-hept-6-enoylmalonamides were prepared and treated with a catalytic amount of rhodium(II) perfluorobutyrate. The resultant carbenoids underwent facile cyclization onto the neighboring amide carbonyl oxygen atom to generate isomunchnone-type intermediates. Subsequent 1,3-dipolar cycloaddition across the pendant olefin afforded intramolecular cycloadducts in high yield. The cascade sequence is simple, direct, and extremely tolerant of structural diversity. Exposure of these cycloadducts to Lewis acids resulted in oxabicyclic ring opening. N-Acyliminium ions of wide structural variety can be easily generated by this sequence of reactions. Different cyclization pathways become available depending on the nature of the substituent group attached to the amide nitrogen. When the tethered group is electrophilic in nature, proton lass from the initially formed N-acyliminium ion occurs rapidly to-give an acyl enamide which undergoes a subsequent cyclization at the electrophilic center.