diethyl 3-tert-butylcyclopent-3-ene-1,1-dicarboxylate

• 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: diethyl 3-tert-butylcyclopent-3-ene-1,1-dicarboxylate
• 化学式: C₁₅H₂₄O₄
• 分子量: 268.353
• InChiKey: RIWCVIQHMHNTRG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  烯丙基丙二酸二乙酯 在 (C(CH₃)(CF₃)2O)2Mo(=N-2,6-(i-Pr)2-Ph)=CH-CPh(CH₃)2 、 sodium ethanolate 作用下， 以 苯 为溶剂， 生成 diethyl 3-tert-butylcyclopent-3-ene-1,1-dicarboxylate
  参考文献：
  名称：

  Effects of Olefin Substitution on the Ring-Closing Metathesis of Dienes

  摘要：

  Ruthenium alkylidene 1 and molybdenum alkylidene 2 have been utilized in the ring-closing metathesis (RCM) of dienes containing gem-disubstituted olefins to yield td-and tetrasubstituted cyclic olefins. Dienes with sterically demanding and/or electron-withdrawing substituents such as Ph, CO2Me, and Bu-t were cyclized successfully with 2, but did not cyclize with 1. Tetrasubstituted cyclic olefins could be formed with 2, but not using alkylidene-1. Dienes with allylic functional groups yielded functionalized cyclic olefins when treated with 1.

  DOI：

  10.1021/jo970877p

文献信息

• Synthesis and Activity of a New Generation of Ruthenium-Based Olefin Metathesis Catalysts Coordinated with 1,3-Dimesityl-4,5-dihydroimidazol-2-ylidene Ligands
  作者：Matthias Scholl、Sheng Ding、Choon Woo Lee、Robert H. Grubbs

  DOI：10.1021/ol990909q

  日期：1999.9.1

  [formula: see text] A new family of 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene-substituted ruthenium-based complexes 9a-c has been prepared starting from RuCl2(=CHPh)(PCy3)2 2. These air- and water-tolerant complexes were shown to exhibit an increased ring-closing metathesis activity at elevated temperature when compared to that of the parent complex 2 and the previously developed complex 3. In many

  [公式：参见文字]从RuCl2（= CHPh）（PCy3）2 2开始，制备了一个新的1,3-二甲磺酰基-4,5-二氢咪唑-2-亚乙基取代的钌基络合物9a-c。与母体复合物2和先前开发的复合物3相比，这些耐空气和水的复合物在升高的温度下显示出更高的闭环易位活性。可以使用低至0.05mol％的催化剂负载量。
• Rendering Schrock-type Molybdenum Alkylidene Complexes Air Stable: User-Friendly Precatalysts for Alkene Metathesis
  作者：Johannes Heppekausen、Alois Fürstner

  DOI：10.1002/anie.201102012

  日期：2011.8.16

  A matter of convenience: Schrock molybdenum alkylidenes are amongst the most powerful olefin metathesis catalysts known to date, but their sensitivity to air and moisture mandates their handling in a glove‐box or by Schlenk techniques. This inconvenience is circumvented by using the corresponding phenanthroline‐ or bipyridine adducts, which are bench‐stable and hence very user‐friendly. The active

  方便的问题：Schrock钼亚烷基是迄今为止已知最强大的烯烃复分解催化剂之一，但它们对空气和湿气的敏感性要求它们在手套箱中或通过Schlenk技术进行处理。使用相应的菲咯啉或联吡啶加合物可以避免这种不便，它们是稳定的，因此非常易于使用。在甲苯中用ZnCl 2处理时，活性物质可以毫不妥协的形式从这些预催化剂中释放出来（参见方案）。
• IMIDAZOLIDINE-BASED METAL CARBENE METATHESIS CATALYSTS
  申请人：CALIFORNIA INSTITUTE OF TECHNOLOGY

  公开号：US20160237101A9

  公开（公告）日：2016-08-18

  The present invention relates to novel metathesis catalysts with an imidazolidine-based ligand and to methods for making and using the same. The inventive catalysts are of the formula wherein: M is ruthenium or osmium; X and X 1 are each independently an anionic ligand; L is a neutral electron donor ligand; and, R, R 1 , R 6 , R 7 , R 8 , and R 9 are each independently hydrogen or a substituent selected from the group consisting of C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, aryloxy, C 2 -C 20 alkoxycarbonyl, C 1 -C 20 alkylthiol, aryl thiol, C 1 -C 20 alkylsulfonyl and C 2 -C 20 alkylsulfinyl, the substituent optionally substituted with one or more moieties selected from the group consisting of C 1 -C 10 alkyl, C 1 -C 10 alkoxy, aryl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen. The inclusion of an imidazolidine ligand to the previously described ruthenium or osmium catalysts has been found to dramatically improve the properties of these complexes. The inventive catalysts maintains the functional group tolerance of previously described ruthenium complexes while having enhanced metathesis activity that compares favorably to prior art tungsten and molybdenum systems.

  本发明涉及一种新型的以咪唑啉为基础的配体的交换催化剂以及其制备和使用方法。该创新催化剂的化学式为：其中，M为钌或锇；X和X1分别为独立的阴离子配体；L为中性电子供体配体；R、R1、R6、R7、R8和R9分别为氢或选自以下基团的取代基：C1-C20烷基、C2-C20烯基、C2-C20炔基、芳基、C1-C20羧酸酯、C1-C20烷氧基、C2-C20烯氧基、C2-C20炔氧基、芳氧基、C2-C20烷氧羰基、C1-C20烷基硫醇、芳基硫醇、C1-C20烷基磺酰基和C2-C20烷基亚磺酰基，所述取代基可选地被一个或多个选自以下基团的取代基所取代：C1-C10烷基、C1-C10烷氧基、芳基和羟基、硫醇、硫醚、酮、醛、酯、醚、胺、亚胺、酰胺、硝基、羧酸、二硫化物、碳酸酯、异氰酸酯、碳酸酰基、卡波酯、卡巴酰胺和卤素的官能团。在以前所述的钌或锇催化剂中加入咪唑啉配体被发现可以显著改善这些配合物的性质。这种创新催化剂保持了以前所描述的钌配合物的官能团耐受性，同时具有增强的交换活性，与先前的钨和钼系统相比具有更好的性能。
• MOLYBDENUM AND TUNGSTEN METAL COMPLEXES AND USE THEREOF AS PRECATALYSTS FOR OLEFIN METATHESIS
  申请人：Furstner Alois

  公开号：US20140296516A1

  公开（公告）日：2014-10-02

  The invention relates to metal complexes of general formula (I) and to a method for the production thereof, in which M, R 1 , R 2 , R 3 , X and Y in addition to R a , R b , R c , R d , R e , R f , R g , R h can have the meanings defined in the claims. Said metal complexes form air-stable compounds and are suitable as pre-catalysts in the olefin metathesis.

  本发明涉及一般式（I）的金属配合物以及其制备方法，其中M，R1，R2，R3，X和Y除了Ra，Rb，Rc，Rd，Re，Rf，Rg，Rh之外可以具有权利要求书中定义的含义。所述金属配合物形成空气稳定的化合物，并适用于烯烃转化的前催化剂。
• Increased ring closing metathesis activity of ruthenium-based olefin metathesis catalysts coordinated with imidazolin-2-ylidene ligands
  作者：Matthias Scholl、Tina M. Trnka、John P. Morgan、Robert H. Grubbs

  DOI：10.1016/s0040-4039(99)00217-8

  日期：1999.3

  The novel air and water tolerant, imidazolinylidene-substituted ruthenium-based complex 3, has been prepared starting from RuCl2(=CHPh)(PCy3)(2) 2 and shown to exhibit increased ring-closing metathesis activity at elevated temperature compared to that of the parent complex 2. Di-, tri-, and even tetra-substituted cycloolefins were successfully prepared from corresponding diene precursors using catalytic amounts of 3 in moderate to excellent yields. (C) 1999 Elsevier Science Ltd. All rights reserved.