(1RS,2SR,4RS)-5-bicyclo<2.2.2>octene-2-carboxaldehyde | 38259-00-6

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氧化物
• 英文名称: (1RS,2SR,4RS)-5-bicyclo<2.2.2>octene-2-carboxaldehyde
• 英文别名: bicyclo[2.2.2]oct-5-en-2-exo-carboxaldehyde；exo-bicyclo[2.2.2]oct-5-ene-2-carbaldehyde；(1RS,2SR,4RS)-5-bicyclo[2.2.2]octene-2-carboxaldehyde；(1S,2R,4S)-Bicyclo[2.2.2]oct-5-ene-2-carbaldehyde
• CAS: 38259-00-6；40570-95-4；57287-40-8；57287-44-2；61949-97-1；128441-67-8
• 化学式: C₉H₁₂O
• 分子量: 136.194
• InChiKey: KCHFYKPIADOPBJ-YIZRAAEISA-N

物化性质

• 沸点：
  204.9±29.0 °C(Predicted)
• 密度：
  1.108±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  1,3-环己二烯 、 丙烯醛 在 erbium(III) triflate 作用下， 反应 4.0h， 以96%的产率得到(1RS,2SR,4RS)-5-bicyclo<2.2.2>octene-2-carboxaldehyde
  参考文献：
  名称：

  Erbium triflate in ionic liquids: A recyclable system of improving selectivity in Diels–Alder reactions

  摘要：

  The efficiency of Er(OTf)(3) in promoting the Diels-Alder reactions between different dienes and dienophiles in ionic liquids has been investigated. Compared with the analogous cycloadditions performed in conventional solvents shorter reaction times are required to obtain good/excellent yields. In most cases an enhancement of regio- and endo:exo selectivity was observed. The role of the ionic liquid, as a function of the cationic part, i.e. the imidazolium based or the pyridinium based, is discussed well. The ILs containing the catalyst can be readily separated from the reaction products and recovered in very high purity for direct reuse, up to six cycles. (C) 2009 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.apcata.2009.10.020

文献信息

• Recyclable organotungsten Lewis acid and microwave assisted Diels–Alder reactions in water and in ionic liquids
  作者：I-Hon Chen、Jun-Nan Young、Shuchun Joyce Yu

  DOI：10.1016/j.tet.2004.09.078

  日期：2004.12

  water-soluble, organotungsten Lewis acid, [OP(2-py)3W(CO)(NO)2](BF4)2 (1), was synthesized and characterized. A series of 1-catalyzed Diels–Alder reactions were investigated under conventional heating or microwave heating conditions. The cycloaddition reactions were efficiently conducted in either water or in an ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate. The ionic liquid acts as a powerful

  合成并表征了水溶性有机钨路易斯酸[OP（2-py）3 W（CO）（NO）2 ]（BF 4）2（1）。在常规加热或微波加热条件下，研究了一系列1催化的Diels–Alder反应。环加成反应在水或离子液体六氟磷酸1-丁基-3-甲基咪唑鎓中有效进行。离子液体不仅用作提高速率和选择性的有力介质，而且还有助于促进催化剂的循环利用。与热加热相比，观察到通过微波闪蒸加热的剧烈速率加速。
• Dramatic acceleration of the Diels-Alder reaction by adsorption on chromatography adsorbents
  作者：V.V. Veselovsky、A.S. Gybin、A.V. Lozanova、A.M. Moiseenkov、W.A. Smit、R. Caple

  DOI：10.1016/s0040-4039(00)80045-3

  日期：1988.1

  The development of a new method for effecting [4+2] cycloadditions on the surface of chromatographic adsorbents in the absence of solvents that leads to a moderation of the reaction conditions and an increase in selectivity is described.

  描述了在不存在溶剂的情况下在色谱吸附剂表面进行[4 + 2]环加成反应的新方法的开发，该方法导致反应条件的缓和和选择性的提高。
• New Strategies for Organic Catalysis:  The First Highly Enantioselective Organocatalytic Diels−Alder Reaction
  作者：Kateri A. Ahrendt、Christopher J. Borths、David W. C. MacMillan

  DOI：10.1021/ja000092s

  日期：2000.5.1

  employ organic molecules as reaction catalysts, 2 despite the widespread availability of organic chemicals in enantiopure form and the accordant potential for academic, industrial, and economic benefit. Herein, we introduce a new strategy for organocatalysis that we expect will be amenable to a range of asymmetric transformations. In this context, we document the first highly enantioselective organocatalytic

  Recei Ved January 7, 2000 在过去的 30 年中，对映选择性催化已成为探索性有机合成研究中最重要的前沿领域之一。在此期间，有机金属不对称催化剂的开发取得了显着进展，进而提供了丰富的对映选择性氧化、还原、π 键活化和路易斯酸催化过程。1 然而，令人惊讶的是，使用有机分子作为反应催化剂的不对称转化相对较少，2 尽管对映纯形式的有机化学品广泛可用，并且具有相应的学术、工业和经济效益潜力。在此，我们介绍了一种新的有机催化策略，我们预计该策略将适用于一系列不对称转化。在这种情况下，我们记录了第一个高度对映选择性的有机催化 Diels-Alder 反应。3
• Catalysis by Organic Solids. Stereoselective Diels−Alder Reactions Promoted by Microporous Molecular Crystals Having an Extensive Hydrogen-Bonded Network
  作者：Ken Endo、Takashi Koike、Tomoya Sawaki、Osamu Hayashida、Hideki Masuda、Yasuhiro Aoyama

  DOI：10.1021/ja964198s

  日期：1997.5.1

  network material shows a novel catalysis in the solid state for the acrolein−cyclohexadiene Diels−Alder reaction. The suggested mechanism involves a catalytic cycle composed of sorption of the reactants in the cavities of polycrystalline host 1, preorganized intracavity reaction, and desorption of the product. The host also promotes stereoselective intracavity reactions for alkyl acrylates and cyclohexadiene

  蒽双间苯二酚衍生物 1 作为一种有机网络材料，在固态下对丙烯醛-环己二烯 Diels-Alder 反应具有新的催化作用。建议的机制涉及催化循环，包括反应物在多晶主体 1 的腔中的吸附、预先组织的腔内反应和产物的解吸。主体还促进丙烯酸烷基酯和环己二烯的立体选择性腔内反应，但在这种情况下，不是以催化方式。本系统作为沸石的功能性有机类似物的相关性根据各个元素过程的动力学和催化剂粉化的影响以及X射线晶体结构进行了讨论。
• Titanium(<scp>IV</scp>) and Zirconium(<scp>IV</scp>) Sulfato Complexes Containing the Kläui Tripodal Ligand: Molecular Models of Sulfated Metal Oxide Surfaces
  作者：Qian-Feng Zhang、Tony C. H. Lam、Xiao-Yi Yi、Eddie Y. Y. Chan、Wai-Yeung Wong、Herman H. Y. Sung、Ian D. Williams、Wa-Hung Leung

  DOI：10.1002/chem.200400853

  日期：2005.1

  [L(OEt)Ti(OTf)(3)] (4), whereas treatment of 2 with Ag(OTf) in CH(2)Cl(2) afforded the sulfato-capped trinuclear complex [(L(OEt))(3)Ti(3)(mu-O)(3)}(mu(3)-SO(4))Ag(OTf)}][OTf] (5), in which the Ag(OTf) moiety binds to a mu-oxo group in the Ti(3)(mu-O)(3) core. Reaction of 2 in H(2)O with Ba(NO(3))(2) afforded the tetranuclear complex (L(OEt))(4)Ti(4)(mu-O)(6) (6). Treatment of 2 with [Rh(cod)Cl}(2)] (cod=1

  用NaL（OEt）（L（OEt）（-）= [（eta（5）-C（5）H（5））Co P（O）（OEt）（ 2）}（3）]（-））提供了mu-硫酸盐络合物[（L（OEt）Ti）（2）（mu-O）（2）（mu-SO（4））]（2）。在更浓的硫酸（> 1 M）中，相同的反应产生了二-氨基硫酸盐络合物[（L（OEt）Ti）（2）（mu-O）（mu-SO（4））（2）] （3）。2与HOTf（OTf =三氟甲磺酸盐，CF（3）SO（3））的反应产生了tris（triflato）络合物[L（OEt）Ti（OTf）（3）]（4），而2与Ag（ CH（2）Cl（2）中的OTf）提供了硫酸根加帽的三核复合物[（L（OEt））（3）Ti（3）（mu-O）（3）}（mu（3）-SO（ 4））Ag（OTf）}] [OTf]（5），其中，Ag（OTf）部分与Ti（3）（mu-O）（3）核中的mu-oxo基结合