(1R,4S,4aS,5R,8S,8aS)-1,4,4a,5,8,8a-hexahydro-1,4:5,8-diepoxynaphthalene-4a,8a-dicarboxylic acid | 10243-56-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 呋喃类
• 英文名称: (1R,4S,4aS,5R,8S,8aS)-1,4,4a,5,8,8a-hexahydro-1,4:5,8-diepoxynaphthalene-4a,8a-dicarboxylic acid
• 英文别名: exo,exo-11,12-dioxatetracyclo[6.2.1.1^3,6.0^2,7]dodeca-4,9-diene 2,7-dicarboxylic acid；1,4,5,8-tetrahydro-1t,4t;5t,8t-diepoxido-naphthalene-4ar,8ac-dicarboxylic acid；1,4,5,8-Tetrahydro-1t,4t;5t,8t-diepoxido-naphthalin-4ar,8ac-dicarbonsaeure
• CAS: 10243-56-8；59823-51-7
• 化学式: C₁₂H₁₀O₆
• 分子量: 250.208
• InChiKey: OPAKOEREOQKBPV-MSPTUIENSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  18.0
• 可旋转键数：
  2.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  93.06
• 氢给体数：
  2.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (1R,4S,4aS,5R,8S,8aS)-1,4,4a,5,8,8a-hexahydro-1,4:5,8-diepoxynaphthalene-4a,8a-dicarboxylic acid 在 乙酸酐 、 三乙胺 作用下， 以 氘代氯仿 为溶剂， 反应 0.08h， 生成 (1α,2β,3α,6α,7β,8α)-11-benzyloxycarbonyl-11-aza-12-oxatetracyclo[6.2.1.1^3,6.0^2,7]dodeca-4,9-diene-2,7-dicarboxylic anhydride
  参考文献：
  名称：

  The preparation of 7-substituted norbornadiene-2,3-dicarboxylic anhydrides and an experimental and theoretical study of their reactivity

  摘要：

  Four new substituted methano-bridged or heteroatom-bridged norbornadienomaleic anhydrides have been prepared and converted to sesquinorbornadiene anhydrides by reaction with cyclic 1,3-dienes. The versatility of parity reversal, in conjunction with N-substituent steric effects, has been used to produce all three possible stereoisomers of the NO-sesquinorbomadiene anhydrides in separate, stereoselective cycloadditions. The anhydrides have been synthesized by cyclization of their diacids (in situ production) or by flash vacuum pyrolysis of their furan adducts (yielding crystalline products); further fragmentation occurs at these or higher temperatures to produce five-membered carbocyclic or heterocyclic anhydrides. Activation energies have been evaluated for the fragmentation and cycloaddition processes using DFT calculations (B3LYP/6-31G*) and these calculations correctly predict, which reaction can be intercepted at the norbornadienomaleic anhydride stage and preferred stereochemistry of cycloadducts. (C) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.03.009
• 作为产物：
  描述：

  呋喃 、 丁炔二酸 在 乙醚 作用下， 生成 (1R,4S,4aS,5R,8S,8aS)-1,4,4a,5,8,8a-hexahydro-1,4:5,8-diepoxynaphthalene-4a,8a-dicarboxylic acid
  参考文献：
  名称：

  呋喃和乙炔二羧酸的狄尔斯-阿尔德加合物的构型

  摘要：

  呋喃和乙炔二羧酸的 Diels-Alder 加合物 (I) 的构型是通过化学和光谱方法建立的，并被发现是 exo-exo (IIa)。

  DOI：

  10.1139/v66-185

文献信息

• A new hydroxy-lactonization of olefinic acids
  作者：James B. Hendrickson、Vishwakarma Singh

  DOI：10.1016/s0040-4039(00)81428-8

  日期：1983.1

  Bicyclic olefin acids afford -hydroxy-lactones with aqueous calcium hypochlorite. Monocyclic and acyclic olefin acids yield mainly the corresponding (opened) dihydroxy acids.

  双环烯烃酸与次氯酸钙水溶液一起提供-羟基-内酯。单环和无环烯烃酸主要产生相应的（开环）二羟基酸。
• PREPARATION AND REACTIVITY OF CERTAIN OXAPOLYCYCLIC SYSTEMS
  作者：Michael Sander、Eckehard Volker Dehmlow

  DOI：10.1080/00304940009356285

  日期：2000.4

  In the course of our studies on the preparation of polyfunctional cis substituted decalins,' we became interested in a group of compounds derived from the dicarboxylic acid 1. This oxapolycyclic system, first described by Diels and Alder,? is obtained from the twofold [4+2] cycloaddition of two equivalents of furan to acetylene dicarboxylic acid.' As the dimethyl ester corresponding to the diacid 1

  在我们对制备多官能顺式取代十氢萘的研究过程中，我们对一组衍生自二羧酸的化合物产生了兴趣 1。这个由 Diels 和 Alder 首次描述的氧多环系统，？由两当量的呋喃与乙炔二羧酸的双重[4+2]环加成反应获得。由于对应于二酸 1 的二甲酯易于发生逆狄尔斯-阿尔德反应，因此选择更稳定的酸酐 2 进行进一步研究。1 到 2 的转化是通过用三氟乙酸酐处理 1 在氯仿中的悬浮液来实现的（方案该方法优于 Warrener 描述的文献程序（SOCl），因为现在敏感化合物的聚合减少到最低限度。
• Exploring the Reactivity of Dioxacyclic Compounds as a Route to Polysubstituted Decalins and Fused Polycycles
  作者：Mark Lautens、Eric Fillion

  DOI：10.1021/jo971567+

  日期：1998.2.1

  and related fused polycyclic systems with control at up to six stereocenters, based on the sequential ring-opening of dioxacyclic templates. We have established that the most useful feature of the reactivity of the dioxacyclic compounds toward the nucleophilic ring-opening reaction is that the first ring-opening reaction is significantly faster than the second allowing the sequential transformation of

  我们已经描述了一种化学，区域和立体控制方法，该方法可简单有效地合成多种顺式十氢萘和相关稠合多环系统，并基于二氧环环模板的连续开环控制多达六个立体中心。我们已经确定，二氧杂环化合物对亲核开环反应的最有用的特征是，第一个开环反应明显快于第二个，从而允许氧杂双环部分的顺序转化。已经证明了顺序开环过程的灵活性及其局限性，并报道了一种新的对映选择性开环模式。对映选择性碱基诱导的去对称作用已成功应用于噻二氧五环，从而使产物在
• Influence of Lewis Acids on the Diels–Alder Reaction. V. The Reaction of Furan with Dimethyl Acetylenedicarboxylate
  作者：A.W. McCulloch、D. G. Smith、A. G. McInnes

  DOI：10.1139/v73-617

  日期：1973.12.15

  The Diels–Alder addition of furan to dimethyl acetylenedicarboxylate (DMAD) affords a monoadduct 1. The position and steric course of further addition of furan to the latter are temperature dependent. At temperatures of 50° or below addition occurs mainly at the activated double bond to give endo-endo4 and endo-exo5 diadducts. At 100° addition occurs at the less substituted double bond of the monoadduct to give analogous endo-endo7 and endo-exo9 diadducts; further addition of furan to the latter at 100° affords four triadducts 12–15. The configurations of all these products were determined by p.m.r. and assignments confirmed by simulation of the spectra.AlCl₃ causes enormous rate enhancement of the Diels–Alder additions of furan to DMAD and to the activated double bond of the monoadduct. In the presence of the Lewis acid the predominant diadduct formed is the endo-exo isomer 5.

  呋喃与二甲基乙炔二羧酸酯（DMAD）的Diels-Alder加成生成单加合物1。后续的呋喃加成位置和立体位阻取决于温度。在50℃以下的温度下，加成主要发生在活化的双键上，生成内内型4和内外型5的二加合物。在100℃时，加成发生在单加合物中较不取代的双键上，生成类似的内内型7和内外型9的二加合物；在100℃下，进一步的呋喃加成形成四种三加合物12-15。所有这些产物的构型都由p.m.r.确定，通过模拟光谱进行确认。AlCl3可以极大地增强呋喃与DMAD以及单加合物上活化的双键的Diels-Alder加成速率。在路易斯酸的存在下，主要形成内外型异构体5的二加合物。
• The synthesis of U-shaped cavity molecules with “inner-surface” functionality
  作者：Ronald N. Warrener、Shudong Wang、Richard A. Russell

  DOI：10.1016/s0040-4020(97)00013-6

  日期：1997.3

  New U-shaped cavity molecules with inner-surface functionalisation, eg 19 and 20, have been prepared by stereoselective reaction of cyclopentadiene onto linear bis-(7-oxanorbomenes) 18 and 17 respectively. The norbornene x-centres of cavity molecules 19, 20 are reacted with DMAD/Ru to yield rigid bis-cyclobutenes 21 and 22 which serve as a common entry point to advanced cavity systems with further inner-surface functionalisation (CO, O, alkene). This is achieved by reaction of 21 or 22 with appropriate cyclic dienes (cyclopentadienones, isobenzofurans, furan and 6,6-dimethylfulvene) in highly specific cycloaddition reactions. (C) 1997 Elsevier Science Ltd.