6-iodo-hex-5-ynenitrile | 256385-75-8

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 6-iodo-hex-5-ynenitrile
• 英文别名: 6-Iodohex-5-ynenitrile
• CAS: 256385-75-8
• 化学式: C₆H₆IN
• 分子量: 219.025
• InChiKey: GMYYFZVFHAVXPK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  6-iodo-hex-5-ynenitrile 在 dimethyl sulfide borane 、 环己烯 、 溶剂黄146 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 以70%的产率得到(Z)-6-iodohex-5-enenitrile
  参考文献：
  名称：

  Palladium-Catalyzed Carbene Insertion and Trapping with Carbon Nucleophiles

  摘要：

  Palladium catalysts are shown to catalyze the three-component coupling of vinyl halides, trimethylsilyldiazomethane, and stabilized carbon nucleophiles. The reaction is believed to proceed through a palladium-carbene intermediate LX(R)Pd=CHSiMe3 that undergoes migration of the vinyl substituent to the electrophilic carbene center to generate an eta(3)-allylpalladium intermediate. The allylpalladium intermediate is attacked by the carbon nucleophile to generate a vinylsilane product.

  DOI：

  10.1021/ol800431w
• 作为产物：
  描述：

  己炔腈 在 N-碘代丁二酰亚胺 、 silver nitrate 作用下， 以 丙酮 为溶剂， 反应 3.0h， 以57%的产率得到6-iodo-hex-5-ynenitrile
  参考文献：
  名称：

  [2 + 2 + 2]环加成反应在温和条件下的无金属合成高度取代的吡啶

  摘要：

  通过炔烃和腈的直接分子间环加成反应合成吡啶是有机合成中的当代挑战。布朗斯台德酸介导的杂炔和腈的正式[2 + 2 + 2]环加成反应在温和条件下进行。这构成了高度取代的吡啶核的模块化方法。

  DOI：

  10.1002/anie.201606604

文献信息

• Photosensitized oxidative addition to gold(i) enables alkynylative cyclization of o-alkylnylphenols with iodoalkynes
  作者：Zhonghua Xia、Vincent Corcé、Fen Zhao、Cédric Przybylski、Agathe Espagne、Ludovic Jullien、Thomas Le Saux、Yves Gimbert、Héloïse Dossmann、Virginie Mouriès-Mansuy、Cyril Ollivier、Louis Fensterbank

  DOI：10.1038/s41557-019-0295-9

  日期：2019.9

  to deliver C(sp)2–C(sp) coupling products after reductive elimination. Mechanistic and modelling studies support that an energy-transfer event takes place, rather than a redox pathway. This particular mode of activation in gold homogenous catalysis was applied in several dual catalytic processes. Alkynylbenzofuran derivatives were obtained from o-alkynylphenols and iodoalkynes in the presence of catalytic

  在过渡金属催化的交叉偶联反应中，最完善的氧化加成-还原消除途径是最受关注的一种。尽管很容易与一系列过渡金属发生，但金（i）配合物显示出不愿进行氧化加成反应，除非使用了金（i）上的特殊配体，试剂或反应条件。在这里，我们表明在可见光照射下，铱光催化剂通过三重态敏化触发了炔碘化物在乙烯基金（i）中间体上的氧化加成反应，从而释放出C（sp）2 -C（sp）还原消除后的偶联产物。机理和模型研究支持发生能量转移事件，而不是氧化还原途径。金均相催化中的这种特定活化方式已应用于几种双重催化过程中。在蓝色发光二极管辐射下，在催化金（i）和铱（iii）配合物的存在下，从邻炔基苯酚和碘代炔烃获得炔基苯并呋喃衍生物。
• Unlocking Migratory Insertion in Gold Redox Catalysis
  作者：Wenliang Wang、Meiling Ding、Chuan‐Gang Zhao、Shuai Chen、Chengjian Zhu、Jie Han、Weipeng Li、Jin Xie

  DOI：10.1002/anie.202304019

  日期：2023.7.17

  Exploration of elementary reactions in organometallic catalysis is an important method with which to discover new reactions. In this article, we report a gold(I)‐catalyzed iodo‐alkynylation of benzyne involving the merging of challenging migratory insertion and an oxidative addition process in gold catalytic cycle. A wide range of structurally diverse alkynyl iodides are good coupling partners in this iodo‐alkynylation transformation. Both aliphatic and aromatic alkynyl iodides can react with benzynes smoothly to afford highly functionalized 1,2‐disubstituted aromatics in moderate to good yields. Its good functional group compatibility and late‐stage application of complex molecules demonstrate its synthetic robustness. Studies of the mechanism reveals the feasibility of oxidative addition and the DFT calculations demonstrate the possible migratory insertion of benzyne into Au^III‐carbon bonds in the Au^I/Au^III redox catalytic cycle, representing an important step towards an elementary reaction in gold chemistry research.

  摘要 探索有机金属催化中的基本反应是发现新反应的重要方法。本文报告了一种金（I）催化的苄基碘炔化反应，涉及金催化循环中具有挑战性的迁移插入和氧化加成过程的合并。在这种碘-炔基转化过程中，多种结构不同的炔基碘化物都是很好的偶联剂。脂肪族和芳香族炔基碘化物都能与苄基化合物顺利发生反应，以中等至良好的收率得到高度官能化的 1,2-二取代芳烃。其良好的官能团兼容性和复杂分子的后期应用证明了它的合成稳定性。对其机理的研究揭示了氧化加成的可行性，而 DFT 计算则证明了在 AuI/AuIII 氧化还原催化循环中，苄基可能会迁移插入 AuIII 碳键，这代表着向金化学研究的基本反应迈出了重要的一步。
• Reactions of Alkenes, Alkynes, and Alkoxyallenes with New Polymer-Supported Electrophilic Reagents
  作者：Holger Monenschein、Georgia Sourkouni-Argirusi、Katherine M. Schubothe、Thomas O'Hare、Andreas Kirschning

  DOI：10.1021/ol991149m

  日期：1999.12.1

  Preparation of new polymer-supported electrophilic reagents that efficiently promote 1,2-haloacetoxylations of alkenes and alkoxyallenes is described. Under very mild conditions and in high yields, alkenes are transformed into or-halo acetates while alkoxyallenes lead to vinyl iodides. In contrast to these results, terminal alkynes commonly afford synthetically valuable l-iodo-alkynes.
• Ferrier-Type Alkynylation Reaction Mediated by Indium
  作者：Nadège Lubin-Germain、Agnès Hallonet、Florent Huguenot、Sara Palmier、Jacques Uziel、Jacques Augé

  DOI：10.1021/ol701480x

  日期：2007.8.1

  An efficient Ferrier-type alkynylation reaction between glycals and iodoalkynes using Barbier conditions is described. These conditions require In-0, In-I, or In-II and lead to alpha-2,3-unsaturated-C-glycosides with good stereoselectivity. When glycosyliodoalkynes are used, trehalose-derived compounds and alpha-(1 -> 6)-C-disaccharides are obtained.