dimethyl 1α,8α,9β,12β-tetracyclo[6.4.1.0^2,7.0^9,12]trideca-2,4,6,10-tetraene-10,11-dicarboxylate | 61697-16-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: dimethyl 1α,8α,9β,12β-tetracyclo[6.4.1.0^2,7.0^9,12]trideca-2,4,6,10-tetraene-10,11-dicarboxylate
• 英文别名: dimethyl (2aα,3β,8β,8aα)-2a,3,8,8a-tetrahydro-3,8-methanocyclobutanaphthalene-1,2-dicarboxylate；dimethyl (2aα,3β,8β,8aα)-2a,3,8,8a-tetrahydro-3,8-methanocyclobuta[b]naphthalene-1,2-dicarboxylate；dimethyl (1R,8S,9R,12S)-tetracyclo[6.4.1.02,7.09,12]trideca-2,4,6,10-tetraene-10,11-dicarboxylate
• CAS: 61697-16-3
• 化学式: C₁₇H₁₆O₄
• 分子量: 284.312
• InChiKey: IAEDQRQELYHOIT-MPZDIEGVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.41
• 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 1α,8α,9β,12β-tetracyclo[6.4.1.0^2,7.0^9,12]trideca-2,4,6,10-tetraene-10,11-dicarboxylate 生成 dimethyl (1S,8R,9S,10R,12S,13R)-11-benzyl-11-azapentacyclo[6.5.1.02,7.09,13.010,12]tetradeca-2,4,6-triene-10,12-dicarboxylate
  参考文献：
  名称：

  扩展的7-Azanorbornanes中的在线邻近效应。1.一种基于N-Invertomer几何结构控制效应基团分离的新概念。

  摘要：

  稠合7-氮杂硼硼烷系统中N取代基几何结构的控制基于一个相对于N桥的邻近桥（前哨X）相对于另一个桥（前哨Y）的优势。N转化平衡可以有效地取代单个转化聚合物。这项研究结合了合成，晶体学和分子模型来建立立体结构。

  DOI：

  10.1021/ol9910969
• 作为产物：
  描述：

  1,4-二氢-1,4-甲桥萘 、 丁炔二酸二甲酯 在 bromotricarbonyl(tetrahydrofuran)rhenium(I) dimer 2-异氰基-1,3-二异丙基苯 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以92%的产率得到dimethyl 1α,8α,9β,12β-tetracyclo[6.4.1.0^2,7.0^9,12]trideca-2,4,6,10-tetraene-10,11-dicarboxylate
  参考文献：
  名称：

  Rhenium-catalyzed [2+2] Cycloadditions of Norbornenes with Internal and Terminal Acetylenes

  摘要：

  在催化量的[ReBr(CO)3(thf)]2存在下，内式和末端乙炔与降冰片烯反应，以优良至优异的产率得到环丁烯衍生物。

  DOI：

  10.1246/cl.2007.1162

文献信息

• Microwave-Accelerated Ruthenium-Catalyzed [2<font>π</font> + 2<font>π</font>] Cycloadditions of Dimethylacetylene Dicarboxylate with Norbornenes
  作者：Davor Margetić、Pavle Trošelj、Yasujiro Murata

  DOI：10.1080/00397911.2010.481744

  日期：2011.3.28

  Abstract An efficient and convenient procedure has been developed for the ruthenium-catalyzed [2π + 2π] cycloadditions of dimethylacetylene dicarboxylate with norbornenes. Reaction is significantly accelerated in microwave conditions, while the commonly used benzene solvent was replaced by environmentally benign tetrahydrofuran.

  摘要 已经开发了一种高效便捷的方法，用于钌催化的二甲炔二甲酸与降冰片烯的 [2π + 2π] 环加成反应。在微波条件下反应显着加速，而常用的苯溶剂被环境友好的四氢呋喃取代。
• A cascade thermal isomerisation of cyclobutane di-(carbomethoxy) Δ2-1,2,3-triazolines with intramolecular 1,3-dipolar cycloreversion as the key step
  作者：Davor Margetić、Ronald N. Warrener、Douglas N. Butler、Chuan-Ming Jin

  DOI：10.1016/j.tet.2012.02.073

  日期：2012.4

  quantum chemical calculations have been used to support a postulated reaction mechanism involving as the first step, a rare example of intramolecular 1,3-dipolar cycloreversion. Subsequently, several steps involving 1,3-dipolar ring closure, hydrogen shifts and an intramolecular addition are postulated leading to the observed product of this deep-seated isomerisation. The influence of changing substituents

  应变Δ的前所未有的热异构化2导致的产物的形成-1,2,3- triazolines具有一种新颖的1,2,7-三氮杂双环[3.3.0]辛-2-烯环在降冰片烷骨架引入系统。实验证据和量子化学计算已用于支持假设的反应机理，该反应机理涉及第一步，分子内1,3-偶极环还原的罕见例子。随后，提出了涉及1,3-偶极环闭合，氢转移和分子内加成的几个步骤，导致观察到这种深层异构化的产物。还研究了取代基的变化对这种新型反应级联产物结果的影响。
• Dipolar Cycloaddition Reactions of Azomethine Ylides Generated by endocyclic-exocyclic 1,3-dipole Rearrangement
  作者：Davor Margetić、Ronald N. Warrener、Douglas N. Butler、Craig M. Holland

  DOI：10.1002/jhet.2167

  日期：2015.9

  Dipolar cycloaddition of polycyclic azomethine ylides, in which the central nitrogen atom is part of a pyrrolidine ring and bears a methoxycarbonyl group with norbornenes has been shown to produce two main types of products featuring pyrrolizidine rings. In conjuction with results of quantum chemical calculations (B3LYP), mechanistic rationale was postulated. The key reaction step is unprecedented

  已显示多环偶氮甲亚胺的双极环加成反应产生两种主要类型的具有吡咯嗪环的产物，其中中心氮原子是吡咯烷环的一部分，并带有降冰片烯。结合量子化学计算（B3LYP）的结果，提出了机械原理。关键的反应步骤是通过分子间的质子迁移（形式[1,3] H位移）实现空前的环内至环外甲亚胺叶立德重排。
• Neighbouring Group Participation in <i>N</i>-Methoxymethyl 7-Azanorbornanes 1: The Synthesis of <i>N,N′</i>-Methano-bridged Diazasesquinorbornanes, N³-[3]Polynorbornanes and CN³-[4]Polynorbornanes
  作者：Ronald N. Warrener、Davor Margetic、Douglas N. Butler、Guangxing Sun

  DOI：10.1055/s-2001-10789

  日期：——

  A new tandem route to N,N′-methano-bridged diazasesquinorbornanes is reported in which 7-azabenzonorbornadienes are reacted with ester-activated N-(methoxymethyl)aziridinocyclobutanes to form adducts which immediately undergo N,N′-methanobridge formation by nucleophilic attack of the nitrogen lone pair of one N-bridge onto the methoxymethyl group attached to the adjacent N-bridge. Alternative routes to N,N′-methano-bridged structures of this type are discussed.

  报告了一种获得 N,N′-甲桥重氮喹硼烷的新串联路线，其中 7-氮杂苯并降冰片二烯与酯活化的 N-(甲氧基甲基)氮丙啶环丁烷反应生成加合物，加合物通过一个 N 桥的氮孤对与连接到相邻 N 桥的甲氧基甲基的亲核攻击立即形成 N,N′-甲桥。本文讨论了形成这种类型的 N,N′-甲桥结构的其他途径。
• Synthesis of a Variety of Bichromophoric “Ball-and-Chain” Systems Based on Buckminsterfullerene (C₆₀) for the Study of Intramolecular Electron and Energy Transfer Processes
  作者：James M. Lawson、Anna M. Oliver、Daniel F. Rothenfluh、Yi-Zhong An、George A. Ellis、Millagahamada G. Ranasinghe、Saeed I. Khan、Andreas G. Franz、Padma S. Ganapathi、Michael J. Shephard、Michael N. Paddon-Row、Yves Rubin

  DOI：10.1021/jo960512p

  日期：1996.1.1

  Diels-Alder reaction of C-60 with the 1,3-dienes 7e-h, 8a, 8b, and 8d-h affords the ''ball-and-chain'' systems 2e-h, 3a, 3b, and 3d-h bearing two chromophores linked via a rigid, hybrid saturated polynorbornane-bicyclo[2.2.0]hexane (''norbornylogous'') hydrocarbon bridge. Analogous reaction with the bis(diene) 9 affords the soluble dumbbell system 4 bearing two C-60, chromophores. The norbornylogous bridge is a strong mediator of electron and energy transfer via a through-bond coupling mechanism. The norbornylogous donor-bridge-diene units 7d-h, 8a, 8b, and 8d-h were prepared in a straightforward manner from bicyclo[2.2.2]octane precursors by extending the bridges with linearly fused norbornane-bicyclo[2.2.0]hexane moieties through execution of the tandem Mitsudo-Smith series of reactions. The X-ray structure of the dimethoxybenzene-bridge-C-60 system 3a reveals favorable self-complementarity manifested by the unusual packing structure of 3a in the crystal. Molecular mechanics, semiempirical, and ab initio conformational analyses of compounds 2e, 3a, 3b, 3e, 3f, 3h, 68, and 70 (MM2, Sybyl, CVFF, AM1, HF/3-21G) were performed to quantify their ability to adopt two nondegenerate boat conformations, i.e,, extended and folded conformers, as well as their kinetic barrier of interconversion. A similar treatment of the C-60-bridge-C-60 system 4 revealed unusual preference for the folded-folded conformer (18.9 kcal/mol at CVFF level), which was not reproduced by the AM1 method (0.11 kcal/mol). The reduction potentials of the systems 2e, 3a, and 3e were about 0.1-0.5 V more negative than C-60, and the third reduction potential (E(3)) Of the 6-bond system 2e was 0.14 V more negative than the corresponding wave for the 10-bond system 3e. This shift was attributed to the closer proximity of the dimethylaniline donor group to the C-60 surface for 2e vs 3e.