4,4-dicarbomethoxy-1,2-dimethylene cyclohexane | 109432-97-5

• 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: 4,4-dicarbomethoxy-1,2-dimethylene cyclohexane
• 英文别名: Dimethyl 3,4-dimethylene-1,1-cyclohexanedicarboxylate；dimethyl 3,4-dimethylidenecyclohexane-1,1-dicarboxylate
• CAS: 109432-97-5
• 化学式: C₁₂H₁₆O₄
• 分子量: 224.257
• InChiKey: MOUFAWLDUXYVRO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4,4-dicarbomethoxy-1,2-dimethylene cyclohexane 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 三(邻甲基苯基)磷 作用下， 以 苯 为溶剂， 生成 5,5-bis(phenylsulfonyl)-1-octen-7-yne
  参考文献：
  名称：

  A new palladium catalyst for intramolecular carbametalations of enynes

  摘要：

  DOI：

  10.1016/s0040-4039(01)80273-2
• 作为产物：
  描述：

  亚甲基丙二酸二甲酯 在 1,4-dihydroquinoline 、 N-溴代丁二酰亚胺(NBS) 、 methyloxirane 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 1.17h， 生成 4,4-dicarbomethoxy-1,2-dimethylene cyclohexane
  参考文献：
  名称：

  2,3-Bis[(trimethylsilyl)methyl]-1,3-butadiene. A conjunctive reagent for tandem Diels-Alder reactions

  摘要：

  DOI：

  10.1021/ja00379a066

文献信息

• A rhodium catalyzed cycloisomerization and tandem Diels–Alder reaction for facile access to diverse bicyclic and tricyclic heterocycles
  作者：Yirong Zhou、Ali Nikbakht、Felix Bauer、Bernhard Breit

  DOI：10.1039/c9sc00980a

  日期：——

  labelling experiments and DFT calculations were performed to provide insights into the reaction mechanism of this unprecedented transformation. In addition, one-pot tandem Diels–Alder reactions with various dienophiles could readily construct diverse bicyclic and tricyclic nitrogen heterocycles, which are ubiquitous core scaffolds for a variety of natural products and bioactives. High efficiency and exclusive

  利用铑/二膦催化剂体系，成功开发了1，6-丙二烯的区域选择性远侧环异构化反应，得到六元环外环1，3-二烯。进行了氘标记实验和DFT计算，以洞察这种前所未有的转化的反应机理。此外，一锅串联Diels-Alder反应与各种亲双烯体反应可以轻松构建各种双环和三环氮杂环，它们是各种天然产物和生物活性物质的普遍存在的核心支架。在温和的条件下，使用0.5 mol％的低催化剂负载量，可在宽广的底物范围内实现高效率以及独特的化学和区域选择性。
• A novel nickel-chromium catalyst system for cyclization via intramolecular carbametalation
  作者：Barry M. Trost、James M. Tour

  DOI：10.1021/ja00251a036

  日期：1987.8
• Pd-Catalyzed Cycloisomerization to 1,2-Dialkylidenecycloalkanes. 2. Alternative Catalyst System
  作者：Barry M. Trost、Donna L. Romero、Frode Rise

  DOI：10.1021/ja00089a016

  日期：1994.5

  The mechanisms by which palladium complexes may catalyze the cycloisomerization of 1,6- and 1,7-enynes to dialkylidenecycloalkanes were probed by exploring a catalyst system different than a ligated palladium acetate which previously has proven to be successful. Although carboxylic acids showed no discernible interaction with palladium(0) complexes, this combination proved to be a powerful catalyst system to effect this cycloisomerization. The fact that the two catalyst systems do not have the same reactivity profile suggests this new catalyst system may operate by a different mechanism. Evidence supporting a pathway invoking formation of a hydridopalladium acetate followed by hydropalladation as initiation is presented. Steric and electronic effects direct the regioselectivity of the termination step to form either 1,3- or 1,4-diene products. The 1,3-diene products participate exceedingly well in Diels-Alder reactions, both inter- and intramolecularly. The presence of an oxygen substituent at the position allylic to the diene served as both a regiochemical control element for the palladium-catalyzed cycloisomerization and a diastereochemical control element for the Diels-Alder reaction. The net result of these two steps, the first of which is a catalyzed isomerization and the second an addition, is a highly efficient approach to complex polycycles in terms of both selectivity and atom economy.
• TROST, BARRY M.;LEE, DONNA C.;RISE, FRODE, TETRAHEDRON LETT., 30,(1989) N, C. 651-654
  作者：TROST, BARRY M.、LEE, DONNA C.、RISE, FRODE

  DOI：——

  日期：——
• A new palladium catalyst for intramolecular carbametalations of enynes
  作者：Barry M. Trost、Donna C. Lee、Frode Rise

  DOI：10.1016/s0040-4039(01)80273-2

  日期：——