2-cyclohexylmethyl-malonic acid dimethyl ester | 217654-79-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2-cyclohexylmethyl-malonic acid dimethyl ester
• 英文别名: dimethyl (cyclohexylmethyl)malonate；Dimethyl 2-(cyclohexylmethyl)propanedioate
• CAS: 217654-79-0
• 化学式: C₁₂H₂₀O₄
• 分子量: 228.288
• InChiKey: IMMXJDKPGOUVGF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 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：

  2-cyclohexylmethyl-malonic acid dimethyl ester 在 tris(dibenzylideneacetone)dipalladium (0) lithium aluminium tetrahydride 、 四丁基氟化铵 、 sodium hydride 、 1,4-双(二苯基膦)丁烷 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 42.5h， 生成 (E)-5-(cyclohexylmethyl)-5-(hydroxymethyl)hex-2-ene-1,6-diol
  参考文献：
  名称：

  钯催化形成环醚 - 反应的区域选择性、立体选择性和对映选择性

  摘要：

  3-烷基-3-羟甲基-5-乙烯基四氢呋喃的有效立体选择性合成是通过 PdO 催化的 ω,ω-双（羟甲基）-α,β-不饱和醇的碳酸甲酯环化反应进行的。手性配体的使用产生了低到中等对映体比率的相应 THF 衍生物。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

  DOI：

  10.1002/ejoc.200601019
• 作为产物：
  描述：

  乙烯基环己烷 以 二氯甲烷 、 丙酮 为溶剂， 反应 36.0h， 生成 2-cyclohexylmethyl-malonic acid dimethyl ester
  参考文献：
  名称：

  亲芳香性通过光激发和氧化实现脱烯基化功能化

  摘要：

  脱烯基化的 Giese 型加成、肼化、硼化、Minisci 型烷基化、铜催化的 NH 烷基化、酰化、炔基化、氰化和叠氮化，已经以一锅法和高度模块化的方式在含烯烃的底物上实现。

  DOI：

  10.1002/chem.202203425

文献信息

• Multi-catalysis cascade reactions based on the methoxycarbonylketene platform: diversity-oriented synthesis of functionalized non-symmetrical malonates for agrochemicals and pharmaceuticals
  作者：Dhevalapally B. Ramachary、Chintalapudi Venkaiah、Y. Vijayendar Reddy、Mamillapalli Kishor

  DOI：10.1039/b901652j

  日期：——

  In this paper we describe new multi-catalysis cascade (MCC) reactions for the one-pot synthesis of highly functionalized non-symmetrical malonates. These metal-free reactions are either five-step (olefination/hydrogenation/alkylation/ketenization/esterification) or six-step (olefination/hydrogenation/alkylation/ketenization/esterification/alkylation), and employ aldehydes/ketones, Meldrum's acid, 1,4-dihydropyridine/o-phenylenediamine, diazomethane, alcohols and active ethylene/acetylenes, and involve iminium-, self-, self-, self- and base-catalysis, respectively. Many of the products have direct application in agricultural and pharmaceutical chemistry.

  在本文中，我们描述了一种新的多重催化级联反应（MCC），用于一锅合成高度功能化的非对称马来酸酯。这些无金属催化反应分为五步（烯化/加氢/烷基化/酮化/酯化）或六步（烯化/加氢/烷基化/酮化/酯化/烷基化），涉及醛/酮、梅尔德伦酸、1,4-二氢吡啶/邻苯二胺、重氮甲烷、醇以及活性乙烯/炔烃，分别涉及亚胺、各自、自我、自我和碱催化。许多产品在农业和制药化学中具有直接应用。
• Enantioselective Synthesis of α-Quaternary Amino Acid Derivatives by Sequential Enzymatic Desymmetrization and Curtius Rearrangement of α,α-Disubstituted Malonate Diesters
  作者：Violeta Iosub、Anton R. Haberl、Jennifer Leung、Michael Tang、Kannan Vembaiyan、Masood Parvez、Thomas G. Back

  DOI：10.1021/jo902584r

  日期：2010.3.5

  A convenient and versatile enantioselective synthesis of biologically important α-quaternary amino acid derivatives was based on the sequential double alkylation or arylation of dimethyl malonate, followed by desymmetrization with porcine liver esterase (PLE) and Curtius rearrangement. The PLE-mediated hydrolysis of the prochiral dialkylated malonate diesters produced the corresponding chiral half-esters

  生物学上重要的α-季氨基酸衍生物的方便且通用的对映选择性合成是基于丙二酸二甲酯的顺序双烷基化或芳基化，然后用猪肝酯酶（PLE）进行不对称化和Curtius重排。PLE介导的前手性二烷基丙二酸二酯的水解以高收率和对映体过量43％至> 98％产生了相应的手性半酯。在用苄醇或胺捕获中间异氰酸酯后，后一种产物的库尔修斯重排得到相应的Cbz-保护的氨基酯或脲。在五个示例中，主要产品的绝对构型是通过转化为具有已知比旋光度的化合物确定的，
• Visible‐Light Photoredox Catalyzed Regioselective 1,4‐Hydroalkylation of 1,3‐Enyne
  作者：Hong Hou、Yingjie Pan、Yuejie Sun、Ying Han、Chaoguo Yan、Yaocheng Shi、Shaoqun Zhu

  DOI：10.1002/chem.202301633

  日期：2023.9.12

  Described herein is a visible‐light photoredox‐catalyzed regioselective 1,4‐hydroalkylation of 1,3‐enynes. Various of di‐ and tri‐substituent allenes were really accessible under the present reaction conditions. The visible‐light photoredox activation of the carbon nucleophile to generate its radical species, allowing the addition with un‐activated enynes. The synthetic utility for the present protocol was demonstrated by a large‐scale reaction, as well as the derivatization of the allene product.

  摘要 本文介绍了一种可见光光氧化催化的 1,3- 烯炔 1,4- 氢化烷基化反应。在目前的反应条件下，确实可以获得各种二取代基和三取代基烯。碳亲核物在可见光光氧化活化后产生自由基，从而可以与未活化的烯炔进行加成反应。通过大规模反应以及烯烃产物的衍生化，证明了本方案的合成实用性。
• METHOD FOR PRODUCING SOLID CATALYST COMPONENT FOR USE IN POLYMERIZATION OF OLEFIN, CATALYST FOR USE IN POLYMERIZATION OF OLEFIN, AND METHOD FOR PRODUCING OLEFIN POLYMER
  申请人：Toho Titanium CO., LTD.

  公开号：EP2876118A1

  公开（公告）日：2015-05-27

  A method for producing a solid catalyst component for olefin polymerization produces a novel solid catalyst component for olefin polymerization that achieves excellent olefin polymerization activity and activity with respect to hydrogen during polymerization, and can produce an olefin polymer that exhibits a high MFR, high stereoregularity, and excellent rigidity. The method includes a first step that brings a magnesium compound, a tetravalent titanium halide compound, and one or more first internal electron donor compounds selected from specific aromatic dicarboxylic diesters into contact with each other to effect a reaction, followed by washing, a second step that brings a tetravalent titanium halide compound and one or more second internal electron donor compounds into contact with a product obtained by the first step to effect a reaction, followed by washing, and a third step that brings one or more third internal electron donor compounds into contact with a product obtained by the second step to effect a reaction.

  一种生产烯烃聚合用固体催化剂组分的方法可生产出一种新型的烯烃聚合用固体催化剂组分，该组分具有优异的烯烃聚合活性和聚合过程中对氢的活性，并可生产出具有高MFR、高立体规整度和优异刚性的烯烃聚合物。该方法包括第一步，使镁化合物、四价卤化钛化合物和一种或多种选自特定芳香族二羧酸二酯的第一内部电子供体化合物相互接触以发生反应，然后进行洗涤、第二步：使四价卤化钛化合物和一种或多种第二内部电子供体化合物与第一步得到的产物接触，以发生反应，然后进行洗涤；第三步：使一种或多种第三内部电子供体化合物与第二步得到的产物接触，以发生反应。
• PRODUCTION METHOD FOR SOLID CATALYST COMPONENT FOR POLYMERIZING OLEFINS, CATALYST FOR POLYMERIZING OLEFINS, AND PRODUCTION METHOD FOR POLYMERIZED OLEFINS
  申请人：TOHO TITANIUM CO., LTD.

  公开号：EP2963063A1

  公开（公告）日：2016-01-06

  A method for producing a solid catalyst component for olefin polymerization produces a novel solid catalyst component for olefin polymerization that achieves excellent olefin polymerization activity and activity with respect to hydrogen during polymerization, and can produce an olefin polymer that exhibits a high MFR, high stereoregularity, and excellent rigidity. The method includes a first step that brings a magnesium compound, a tetravalent titanium halide compound, and one or more first internal electron donor compounds excluding an aromatic dicarboxylic acid diester into contact with each other to effect a reaction, followed by washing; a second step that brings a tetravalent titanium halide compound and one or more second internal electron donor compounds into contact with a product obtained by the first step to effect a reaction, followed by washing; and a third step that brings one or more third internal electron donor compounds into contact with a product obtained by the second step to effect a reaction.

  一种生产烯烃聚合用固体催化剂组分的方法可生产出一种新型的烯烃聚合用固体催化剂组分，该组分具有优异的烯烃聚合活性和聚合过程中对氢的活性，并可生产出具有高MFR、高立体规整度和优异刚性的烯烃聚合物。该方法包括第一步，使镁化合物、四价卤化钛化合物和一种或多种第一内部电子供体化合物（不包括芳香族二羧酸二酯）相互接触以发生反应，然后进行洗涤；第二步，使四价卤化钛化合物和一种或多种第二内部电子供体化合物与第一步得到的产物接触，以发生反应，然后进行洗涤；以及第三步，使一种或多种第三内部电子供体化合物与第二步得到的产物接触，以发生反应。