dimethyl bicyclo[4.1.0]heptane-7,7-dicarboxylate | 34916-57-9

• 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: dimethyl bicyclo[4.1.0]heptane-7,7-dicarboxylate
• 英文别名: 7,7-dimethoxycarbonylbicyclo[4.1.0]heptane
• CAS: 34916-57-9
• 化学式: C₁₁H₁₆O₄
• 分子量: 212.246
• InChiKey: NKYDQIONNPENJX-UHFFFAOYSA-N

物化性质

• 熔点：
  83-85 °C(Solv: ethyl ether (60-29-7))
• 沸点：
  246.0±13.0 °C(Predicted)
• 密度：
  1.186±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 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：

  dimethyl bicyclo[4.1.0]heptane-7,7-dicarboxylate 在 氢氧化钾 作用下， 以 甲醇 、 水 为溶剂， 反应 24.0h， 以97%的产率得到bicyclo[4.1.0]heptane-7,7-dicarboxylic acid
  参考文献：
  名称：

  Desymmetrization of spiro-activated meso-cyclopropanes via nucleophilic substitution

  摘要：

  The spiro-activated cyclopropane 1 undergoes desymmetrization either with Li-thiophenoxide in the presence of a chiral complexing ligand, or with ion pairs formed from thiophenols and aromatic chiral amines. The latter procedure is more efficient and provides the ring-opened thioether 6 in up to 79% yield and up to 60% ee. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.03.005
• 作为产物：
  描述：

  丙二酸二甲酯 在 Cu catalyst 对甲苯磺酰叠氮 、 六氟苯 、 三乙胺 作用下， 以 苯 为溶剂， 生成 dimethyl bicyclo[4.1.0]heptane-7,7-dicarboxylate
  参考文献：
  名称：

  The Soluble Copper(I)-Catalyzed Decomposition of Dimethyl Diazomalonate and Di-t-butyl Diazomalonate in the Presence of Some Cycloalkenes

  摘要：

  DOI：

  10.1055/s-1971-21790

文献信息

• Formal Insertion of Thioketenes into Donor–Acceptor Cyclopropanes by Lewis Acid Catalysis
  作者：André U. Augustin、Marius Busse、Peter G. Jones、Daniel B. Werz

  DOI：10.1021/acs.orglett.7b03961

  日期：2018.2.2

  Donor–acceptor cyclopropanes were reacted under Lewis acid catalysis with 3-thioxocyclobutanones as surrogates for disubstituted thioketenes. A broad scope of 2-substituted tetrahydrothiophenes with a semicyclic double bond was obtained under mild conditions with high functional group tolerance and in excellent yield. A sequence of a formal [3 + 2]-cycloaddition followed by the subsequent release of

  供体-受体环丙烷在路易斯酸催化下与3-硫代氧代环丁酮作为双取代硫代乙烯酮的代用品反应。在温和的条件下，具有高官能团耐受性和优异的收率，获得了具有半环双键的2-取代四氢噻吩。推测有一个正式的[3 + 2]-环加成序列，然后随后释放出二取代的乙烯酮作为该机理。
• Design, Preparation, X-ray Crystal Structure, and Reactivity of <i>o</i>-Alkoxyphenyliodonium Bis(methoxycarbonyl)methanide, a Highly Soluble Carbene Precursor
  作者：Chenjie Zhu、Akira Yoshimura、Lei Ji、Yunyang Wei、Victor N. Nemykin、Viktor V. Zhdankin

  DOI：10.1021/ol301268j

  日期：2012.6.15

  The preparation, X-ray structure, and reactivity of new, highly soluble, and reactive iodonium ylides derived from malonate methyl ester and bearing an ortho substituent on the phenyl ring are reported. These new reagents show higher reactivity than common phenyliodonium ylides in the Rh-catalyzed cyclopropanation, C–H insertion, and transylidation reactions under homogeneous conditions.

  报道了衍生自丙二酸酯甲酯且在苯环上带有邻位取代基的新型，高度可溶性和反应性碘鎓的制备，X射线结构和反应性。这些新试剂在均相条件下，在Rh催化的环丙烷化，CH插入和酰化反应中显示出比普通苯基碘鎓碘化物更高的反应性。
• Stereospecific Reactions of Donor-Acceptor Cyclopropanes with Thioketones: Access to Highly Substituted Tetrahydrothiophenes
  作者：André U. Augustin、Maximilian Sensse、Peter G. Jones、Daniel B. Werz

  DOI：10.1002/anie.201708346

  日期：2017.11.6

  Lewis‐acid‐catalyzed reactions of 2‐substituted cyclopropane 1,1‐dicarboxylates with thioketones are described. Highly substituted tetrahydrothiophenes with two adjacent quaternary carbon atoms were obtained in a stereospecific manner under mild conditions and in high yield when using AlCl3 as Lewis acid. Moreover, an intramolecular approach was successfully implemented to gain access to sulfur‐bridged

  描述了路易斯酸催化的2-取代的环丙烷1,1-二羧酸酯与硫酮的反应。当使用AlCl 3作为路易斯酸时，在温和的条件下以立体有择的方式高产率地获得了具有两个相邻的季碳原子的高度取代的四氢噻吩。此外，成功地采用了分子内方法来获得硫桥[ n .2.1]双环系统。在类似条件下，硒酮（较重的类似物）的转化导致形成各种四氢硒代苯。
• RhII-Catalyzed Thermal Cyclopropanations of a Phenyliodonium Bis(carbomethoxy)methylide with Alkenes and Dienes
  作者：Georgia Georgakopoulou、Christos Kalogiros、Lazaros P. Hadjiarapoglou

  DOI：10.1055/s-2001-18750

  日期：——

  Iodonium ylide 2, derived from dimethyl malonate, undergoes facile thermal cycloaddition with alkenes and dienes catalyzed with Rh2(OAc)4 to form the corresponding cyclopropanedicarboxylates and vinylcyclopropanedicarboxylates, respectively, in excellent yields.

  由二甲基美克酸酯衍生的碘阳离子亚胺2，在Rh2(OAc)4催化下与烯烃和二烯发生简便的热环加成反应，分别生成相应的环丙烷二羧酸酯和乙烯基环丙烷二羧酸酯，产率优异。
• <i>S,C</i>-Sulfonium Ylides from Thiophenes:  Potential Carbene Precursors
  作者：Stacey A. Stoffregen、Melanie Heying、William S. Jenks

  DOI：10.1021/ja076351w

  日期：2007.12.1

  Photolysis of S,C-sulfonium ylides derived from thioanisol, thiophene, benzothiophene, or dibenzothiophene provides products deriving from dicarbomethoxycarbene. In methanol, no rearrangement of the carbene to the ketene derivative is observed. Formation of dibenzothiophene and benzothiophene is quantitative. For the thiophene-based ylide, insertion of the carbene into the alpha-CH bond of thiophene

  从苯硫醚、噻吩、苯并噻吩或二苯并噻吩衍生的 S,C-锍叶立德的光解提供衍生自二碳甲氧基卡宾的产物。在甲醇中，没有观察到卡宾重排为烯酮衍生物。二苯并噻吩和苯并噻吩的形成是定量的。对于基于噻吩的叶立德，观察到卡宾插入到噻吩的 α-CH 键中。提供了支持形成单线态和三线态卡宾的证据。