2-allyl-2-ethoxycarbonyl-4-methylene-pentanedioic acid 1-ethyl ester 5-methyl ester | 143208-10-0

• 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: 2-allyl-2-ethoxycarbonyl-4-methylene-pentanedioic acid 1-ethyl ester 5-methyl ester
• 英文别名: 1,6-Heptadiene-2,4,4-tricarboxylic acid, 4,4-diethyl 2-methyl ester；3-O,3-O-diethyl 1-O-methyl hepta-1,6-diene-1,3,3-tricarboxylate
• CAS: 143208-10-0
• 化学式: C₁₅H₂₂O₆
• 分子量: 298.336
• InChiKey: KMVRSSKWGKIWSW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  21
• 可旋转键数：
  12
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2-allyl-2-ethoxycarbonyl-4-methylene-pentanedioic acid 1-ethyl ester 5-methyl ester 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) Oxone 、 碳酸氢钠 作用下， 以 水 、 乙酸乙酯 、 乙腈 为溶剂， 生成 3-hydroxy-4-oxo-cyclopentane-1,1,3-tricarboxylic acid diethyl ester methyl ester
  参考文献：
  名称：

  Ruthenium-Catalyzed Tandem Olefin Metathesis−Oxidations

  摘要：

  The utility of Grubbs' 2nd generation metathesis catalyst has been expanded by the development of two tandem olefin metathesis/oxidation protocols. These ruthenium-catalyzed processes provide cis-diols or r-hydroxy ketones from simple olefinic starting materials.

  DOI：

  10.1021/ol061837n
• 作为产物：
  描述：

  烯丙基丙二酸二乙酯 在 sodium ethanolate 、 potassium carbonate 作用下， 以 丙酮 为溶剂， 反应 24.0h， 生成 2-allyl-2-ethoxycarbonyl-4-methylene-pentanedioic acid 1-ethyl ester 5-methyl ester
  参考文献：
  名称：

  Effects of Olefin Substitution on the Ring-Closing Metathesis of Dienes

  摘要：

  Ruthenium alkylidene 1 and molybdenum alkylidene 2 have been utilized in the ring-closing metathesis (RCM) of dienes containing gem-disubstituted olefins to yield td-and tetrasubstituted cyclic olefins. Dienes with sterically demanding and/or electron-withdrawing substituents such as Ph, CO2Me, and Bu-t were cyclized successfully with 2, but did not cyclize with 1. Tetrasubstituted cyclic olefins could be formed with 2, but not using alkylidene-1. Dienes with allylic functional groups yielded functionalized cyclic olefins when treated with 1.

  DOI：

  10.1021/jo970877p

文献信息

• Microwave enabled external carboxymethyl substituents in the ring-closing metathesis
  作者：Cangming Yang、William V. Murray、Lawrence J. Wilson

  DOI：10.1016/s0040-4039(03)00083-2

  日期：2003.2

  carboxymethyl substituent is presented. The reaction is enabled through microwave irradiation allowing greatly enhanced yields and conversion rates. The reaction results in the formation of carboxymethyl substituted dihydropyrroles, dihydrofurans, and cyclopentenes. In certain cases, pyrroles are formed through further in situ oxidation.

  提出了含有外部羧甲基取代基的二烯烃底物的闭环易位。通过微波辐射使反应得以实现，从而大大提高了产率和转化率。该反应导致羧甲基取代的二氢吡咯，二氢呋喃和环戊烯的形成。在某些情况下，吡咯通过进一步原位氧化形成。
• Nickel-promoted intramolecular cyclization of vinyl bromides with alkenes and alkynes
  作者：Amadeu Llebaria、Francisco Camps、Josep Ma Moretó

  DOI：10.1016/s0040-4039(00)92536-x

  日期：1992.6

  The reaction of vinyl bromides bearing distal olefin or acetylene functionalities with tetracarbonylnickel in the presence of alcohols and triethylamine results in the formation of exo-methylene cyclic esters in a regioselective process. High influence of the bulkiness of the alcohol is found.

  在醇和三乙胺的存在下，带有远端烯烃或乙炔官能团的溴化乙烯与四羰基镍的反应在区域选择性过程中形成外亚甲基环状酯。发现醇的松散度的高度影响。
• Chemoselective ring construction from unsymmetrical 1,6-dienes via radical addition of sulfonyl halides
  作者：I. De Riggi、S. Gastaldi、J. M. Surzur、M. P. Bertrand、Albert Virgili

  DOI：10.1021/jo00049a014

  日期：1992.11

  The sulfonyl radical-promoted cyclizations of 1,6-unsymmetrical dienes can be totally chemoselective. The addition of tosyl halides to various 1,6-dienes bearing both a nucleophilic and an electrophilic double bond clearly indicates that this attractive property is not related to the generally accepted electrophilic nature of tosyl radical. The chemoselectivity is likely to originate from the reversibility of the first step, i.e. tosyl radical addition to the double bond, which favors the formation of the adducts resulting from the one intermediate radical that cyclizes faster.
• De Riggi I., Gastaldi S., Surzur J.-M., Bertrand M. P., Virgili Albert, J. Org. Chem., 57 (1992) N 23, S 6118-6125
  作者：De Riggi I., Gastaldi S., Surzur J.-M., Bertrand M. P., Virgili Albert

  DOI：——

  日期：——
• Effects of Olefin Substitution on the Ring-Closing Metathesis of Dienes
  作者：Thomas A. Kirkland、Robert H. Grubbs

  DOI：10.1021/jo970877p

  日期：1997.10.1

  Ruthenium alkylidene 1 and molybdenum alkylidene 2 have been utilized in the ring-closing metathesis (RCM) of dienes containing gem-disubstituted olefins to yield td-and tetrasubstituted cyclic olefins. Dienes with sterically demanding and/or electron-withdrawing substituents such as Ph, CO2Me, and Bu-t were cyclized successfully with 2, but did not cyclize with 1. Tetrasubstituted cyclic olefins could be formed with 2, but not using alkylidene-1. Dienes with allylic functional groups yielded functionalized cyclic olefins when treated with 1.