1,4-dicyclopentylbuta-1,3-diyne | 134889-83-1

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 1,4-dicyclopentylbuta-1,3-diyne
• 英文别名: 4-Cyclopentylbuta-1,3-diynylcyclopentane；4-cyclopentylbuta-1,3-diynylcyclopentane
• CAS: 134889-83-1
• 化学式: C₁₄H₁₈
• 分子量: 186.297
• InChiKey: WZGCRWLSKVBFDT-UHFFFAOYSA-N

物化性质

• 沸点：
  313.6±9.0 °C(Predicted)
• 密度：
  0.98±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1,4-dicyclopentylbuta-1,3-diyne 在 乙二醇二甲醚溴化镍 、 五甲基二乙烯三胺 、 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 20.0~50.0 ℃ 、506.62 kPa 条件下， 反应 5.0h， 生成 (E)-2-cyclopentylmethylene-4-cyclopentyl-3-butynoic acid methyl ester
  参考文献：
  名称：

  Activation of carbon dioxide: nickel-catalyzed electrochemical carboxylation of diynes

  摘要：

  The simultaneous activation of carbon dioxide and diynes by electrogenerated LNi(0) complexes (L = bpy, pentamethyldiethylenetriamine: PMDTA) enables the selective incorporation of one molecule of CO2 into the unsaturated systems and the preparative-scale electrosyntheses of carboxylic acids. A series of nonconjugated diynes afforded selectively linear or cyclic adducts depending on the ligand. Diynes bearing both a terminal and an internal triple bond gave exclusive CO2 incorporation into the terminal alkynyl group, regioselectively at the 2-position. The electrocarboxylation of 1,3-diynes with the Ni-PMDTA catalytic system yielded, regio- and stereoselectively, (E)-2-vinylidene-3-yne carboxylic acids in one step. The electrosyntheses were carried out in single-compartment cells fitted with a consumable magnesium anode, and utilized a catalytic amount of an air-stable Ni(II) complex as the catalyst precursor. Cyclic voltammetry studies revealed that both carbon dioxide and the diynes are able to coordinate to LNi(0)-generated species in DMF.

  DOI：

  10.1021/jo00061a038
• 作为产物：
  描述：

  4-cyclopentyl-1,1,1-trifluorobut-3-yn-2-one 在 2,2'-联吡啶 、 copper(l) chloride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 6.0h， 以86%的产率得到1,4-dicyclopentylbuta-1,3-diyne
  参考文献：
  名称：

  在温和条件下通过CC键活化的铜介导的壬酸脱酰基偶联。

  摘要：

  通过温和的反应条件下的CuCl-bpy系统完成了未应变的炔酮通过CC键活化的分子间脱酰基反应。该协议的特点是在室温下容易裂解CC键，广泛的底物范围，以及通过炔酮的均相或交联分别有效构建重要的对称和不对称1,3-二炔加合物的方法。初步的机械研究表明，此过程可能涉及酰基铜（III）配合物。

  DOI：

  10.1021/acs.orglett.9b03684

文献信息

• Cobalt Catalyzed, Regioselective C(<i>sp</i>²)–H Activation of Amides with 1,3-Diynes
  作者：Subban Kathiravan、Ian A. Nicholls

  DOI：10.1021/acs.orglett.7b02119

  日期：2017.9.15

  functional class of interest in a range of application areas, to form isoquinolinones—an important structural motif in a number of biologically active substances—is presented. This versatile and inexpensive catalyst employs a covalently attached bidendate-directing group, 8-aminoquinoline. The template directs the C–H activation and facilitates the synthesis of a wide range of alkynylated heterocycles

  开发了第一排过渡金属（钴）基催化剂，用于尚未开发的由C–H活化驱动的1,3-二炔（本身在一系列应用领域中都属于重要的功能类别）反应，以形成异喹啉酮—介绍了许多生物活性物质中的重要结构基序。这种通用且便宜的催化剂采用了共价连接的二齿导向基团8-氨基喹啉。该模板指导C–H活化，并促进在温和条件下具有出色的区域选择性的各种炔基化杂环的合成。该策略为双歧杂环合成的后期应用提供了一种新颖且有效的途径，可用于开发各种杂环框架。
• First example of direct carbon dioxide incorporation into 1,3-diynes: a highly regio- and stereo-selective nickel-catalysed electrochemical reaction
  作者：Sylvie Dérien、Jean-Claude Clinet、Elisabet Duñach、Jacques Périchon

  DOI：10.1039/c39910000549

  日期：——

  The electrosynthesis of 2-vinylidene-3-yne carboxylic acids from carbon dioxide and substituted 1,3-diynes is catalysed by a nickel–triamine complex and results in a regio- and stereo-selective addition to one triple bond.

  从二氧化碳和取代的1,3-二炔合成2-乙烯基-3-炔羧酸的电合成反应，在镍-三胺配合物的催化下，结果是对一个三键的区域选择性和立体选择性加成。
• Radical <i>trans</i>-Hydroboration of Substituted 1,3-Diynes with an <i>N</i>-Heterocyclic Carbene Borane
  作者：Kosuke Takahashi、Steven J. Geib、Katsuhiro Maeda、Dennis P. Curran、Tsuyoshi Taniguchi

  DOI：10.1021/acs.orglett.0c04284

  日期：2021.2.5

  Monohydroboration of substituted 1,3-diynes with an N-heterocyclic carbene borane (NHC–borane) occurs under radical conditions using an azo initiator, such as ACCN and AIBN, and a thiol as a polarity-reversal catalyst. The reaction is highly regio- and stereoselective and provides stable NHC-(E)-alkynylalkenylboranes.

  在自由基条件下，使用偶氮引发剂（如ACCN和AIBN）和硫醇作为极性反转催化剂，可将N-杂环卡宾硼烷（NHC-硼烷）取代的1,3-二炔单氢硼化。该反应是高度区域和立体选择性的，并提供稳定的NHC-（E）-炔基烯基硼烷。
• Transition Metal‐Free Regio‐ and Stereo‐Selective <i>trans</i> Hydroboration of 1,3‐Diynes: A Phosphine‐Catalyzed Access to ( <i>E</i> )‐1‐Boryl‐1,3‐Enynes
  作者：Swetha Jos、Connor Szwetkowski、Carla Slebodnick、Robert Ricker、Ka Lok Chan、Wing Chun Chan、Udo Radius、Zhenyang Lin、Todd B. Marder、Webster L. Santos

  DOI：10.1002/chem.202202349

  日期：2022.11.11

  A transition metal-free method for the trans-hydroboration of 1,3-diynes to afford (E)-1-boryl-1,3-enynes is reported. Boron adds to the external carbon of the diyne framework. Experimental and DFT studies suggest that phosphine attack on the diyne is a key step in the catalytic cycle.

  报道了一种无过渡金属的 1,3-二炔反式硼氢化反应得到 ( E )-1-硼基-1,3-烯炔的方法。硼添加到二炔骨架的外部碳中。实验和 DFT 研究表明，膦对二炔的攻击是催化循环中的关键步骤。
• Sonogashira cross-coupling in a designer ionic liquid (IL) without copper, external base, or additive, and with recycling and reuse of the IL
  作者：A. Srinivas Reddy、Kenneth K. Laali

  DOI：10.1016/j.tetlet.2015.06.067

  日期：2015.8

  Application of a piperidine-appended dimethyl-imidazolium-NTf2 ionic liquid as dual solvent and base in the Sonogashira cross-coupling reaction of aryl-iodides with terminal acetylenes under mild conditions has been demonstrated. The method employs PdCl2(PPh3)(2) without copper and external base. It is applicable to the synthesis of SF5-substituted diaryl- and aryl-alkyl-acetylenes, and can also be utilized for efficient homo-coupling of terminal acetylenes under aerobic conditions. The potential for recycling and reuse of this designer-IL offers an added advantage. (C) 2015 Elsevier Ltd. All rights reserved.