((3-iodophenyl)ethynyl)trimethylsilane | 144001-07-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: ((3-iodophenyl)ethynyl)trimethylsilane
• 英文别名: 2-(3-iodophenyl)ethynyl-trimethylsilane
• CAS: 144001-07-0
• 化学式: C₁₁H₁₃ISi
• 分子量: 300.214
• InChiKey: BHWJVQOQOWIBHI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.52
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 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：

  ((3-iodophenyl)ethynyl)trimethylsilane 在 copper(l) iodide 、 Pb(dba)2 、 potassium carbonate 、 三乙胺 、 三苯基膦 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 、 碘甲烷 作用下， 以 甲醇 、 二氯甲烷 、 苯 为溶剂， 反应 49.0h， 生成
  参考文献：
  名称：

  Geometrically-Controlled and Site-Specifically-Functionalized Phenylacetylene Macrocycles

  摘要：

  A convergent, stepwise synthesis of linear phenylacetylene sequences (PASs) is described. The methodology allows for complete control over chain length, sequence order of monomers, and functional group placement. Chain growth follows geometric progression thus allowing sequences of length 2(n), where n is the number of repetitive cycles, to be assembled in a total of just 3.n steps (two deprotections and one coupling for each cycle). Sequences of length other than 2(n) as well as sequences having a particular arrangement of co-monomer units, can also be realized by merging parallel repetitive cycles. Upon deprotection of the termini, these PASs can be cyclized to phenylacetylene macrocycles (PAMs) in high yield. Control over the ring structure of PAMs is determined by the chemistry of precursor PASs; the size of the macrocycle is related to the sequence length, while the geometry of the macrocycle and the position of the pendant functional groups on the macrocycle is governed by co-monomer sequence order. PAMs with four, five, six, seven, and twelve phenylacetylene monomer units, as well as a variety of site-specifically-functionalized PAMs, have been synthesized with this method. Finally, functional group transformations have been performed on some of the PAMs which lead to PAMs with new functionality. The versatile and efficient approach to this family of geometrically well-defined macrocycles offers potential for producing st set of modular building blocks to rationally assemble molecular crystals and liquid crystals. For this reason, the solid-state characteristics of the hydrocarbon skeletons are of interest. In spite of their solubility in common solvents, hydrocarbon PAMs are shown to yield crystals with remarkable thermal stability and high melting points. Three PAM hydrocarbons are shown not to exhibit melting transitions up to ca 400 degrees C, at which point an abrupt thermal irreversible reaction occurs, apparently involving a solid-state polymerization of the acetylene units.

  DOI：

  10.1021/ja00089a012
• 作为产物：
  描述：

  2-[(三甲基甲硅烷基)乙炔基]苯胺 在 盐酸 、 potassium iodide 、 sodium nitrite 作用下， 生成 ((3-iodophenyl)ethynyl)trimethylsilane
  参考文献：
  名称：

  Selective and efficient access to ortho, meta and para ring-substituted phenylacetylene derivatives R-[CC-C6H4]x-Y (Y : H, NO2, CN, I, NH2)

  摘要：

  ortho, meta and para isomers of iodo and amino ring-substituted phenylacetylene as well as rod-like arylacetylene derivatives were prepared by a simple synthetic route involving three consecutive reactions: the palladium-catalysed carbon-carbon bond formation, the Sandmeyer reaction and thr desilylation of die protected trimethylsilylalkynes. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(97)00451-1

文献信息

• Photoredox mediated C N cross coupling of sulfoximines with aryl iodides
  作者：Sudhir Hande、Adelphe Mfuh、Scott Throner、Ye Wu、Qing Ye、XiaoLan Zheng

  DOI：10.1016/j.tetlet.2019.151100

  日期：2019.10

  A new photoredox-catalyzed CN coupling reaction of sulfoximines with aryl halides has been developed for a general N-arylation of sulfoximines. The reactions proceed in the presence of visible light with high levels of chemoselectivity and a wide range of functionality is tolerated. There is a rapidly increasing interest in sulfoximines as pharmacophores in drug discovery and this new method offers

  已经开发了新的光氧化还原催化的亚砜亚砜与芳基卤化物的C N偶联反应，用于亚砜亚砜的一般N-芳基化。反应在具有高化学选择性水平的可见光存在下进行，并且宽泛的功能性是可以容忍的。在药物发现中，对亚砜亚砜作为药效团的兴趣迅速增长，这种新方法在高官能团耐受性和化合物的后期官能化方面提供了潜力。
• Efficient Synthesis of a Complete Donor/Acceptor <i>bis</i>(Aryl)diyne Family
  作者：Brian T. Holmes、William T. Pennington、Timothy W. Hanks

  DOI：10.1081/scc-120021834

  日期：2003.1.8

  Abstract A facile route to a family of bis(aryl)diynes containing both an electron donating pyridine ring and an electron accepting iodobenzene has been developed. The convergent synthesis involves the coupling of 2-, 3-, or 4-bromopyridine with TMS-acetylene, followed by deprotection to form the first half of the molecule. Similarly, 2-, 3-, or 4-iodoaniline was coupled to TMS-acetylene after protection

  摘要 已经开发了一条合成双（芳基）二炔族的简便途径，该族同时包含一个给电子吡啶环和一个接受电子的碘苯。收敛合成包括将 2-、3- 或 4-溴吡啶与 TMS-乙炔偶联，然后去保护以形成分子的前半部分。类似地，在将胺基保护为二乙基三嗪之后，将 2-、3- 或 4-碘苯胺偶联到 TMS-乙炔上。在将三嗪转化为碘、乙炔脱保护并形成相应的溴苯基乙炔后，分子的两半在 Cadiot-Chodkiewicz 条件下偶联。制备了九种新化合物，发现每种化合物都可以从熔体中热聚合。没有一种化合物在固态下进行光化学聚合。
• Assembly of Layer-Type Organosilver(I) Complexes Incorporating Nitrate and Isomeric Halophenylethynide Ligands
  作者：Ping-Shing Cheng、Sam C. K. Hau、Thomas C. W. Mak

  DOI：10.1071/ch14326

  日期：——

  Single-crystal X-ray analysis of a series of 10 silver(i) nitrate complexes containing carbon-rich ligands each composed of a halosubstituted phenyl nucleus bearing a terminal ethynyl group at various positions provided detailed information on the influence of ligand disposition and orientation, coordination preferences, and the co-existence of silver(i)–ethynide and silver(i)–halogen interactions in the construction of coordination networks, which are consolidated by argentophilic and weak intra or intermolecular interactions.

  对一系列 10 个硝酸银（i）配合物进行了单晶 X 射线分析，这些配合物含有富碳配体，每个配体都由一个卤代苯基核组成，在不同位置上带有一个末端乙炔基，分析结果详细说明了配体排列和取向、配位偏好以及银（i）-乙炔和银（i）-卤素相互作用在配位网络构建过程中的影响，配位网络由亲精作用和微弱的分子内或分子间相互作用加以巩固。
• Catalytic Three-Component Machinery: Control of Catalytic Activity by Machine Speed
  作者：Indrajit Paul、Abir Goswami、Nikita Mittal、Michael Schmittel

  DOI：10.1002/anie.201709644

  日期：2018.1.2

  organocatalyst to DS1–DS3 generates catalytic three‐component machineries. By using a conjugate addition as a probe reaction, we observed a correlation between the operating speed of the slider‐on‐deck systems and the yields of the catalytic reaction. As the thermodynamic binding of the slider decreases, both the frequency of the sliding motion and the yield of the catalytic reaction increase.

  从滑块S1 - S3和甲板D及其三个锌卟啉（ZnPor）结合位点获得了三个超分子甲板上系统DS1 - DS3，作为两组分聚集体。两脚滑子与平台的结合随吡啶/嘧啶（pyr）脚的供体质量和空间位阻而变化，并且受两个N pyr →ZnPor相互作用的影响。因此，滑块以不同的速度，即在室温下以32.2、220和440 kHz的速度在甲板上的三种锌卟啉上移动。在DS1 – DS3中添加N-甲基吡咯烷作为有机催化剂产生催化三组分机械。通过使用共轭加成作为探针反应，我们观察到了甲板上滑模系统的运行速度与催化反应的产率之间的相关性。随着滑块的热力学结合减小，滑动的频率和催化反应的产率均增加。
• Selective Deprotection of Me₃Si-/Ph₂P(O)-protected Arylalkynes: Methyl Grignard Reagent-promoted Dephosphorylation of Ph₂P(O)-protected Alkynes
  作者：Lifen Peng、Feng Xu、Kenta Shinohara、Akihiro Orita、Junzo Otera

  DOI：10.1246/cl.140579

  日期：2014.10.5

  A Ph2P(O)-protected alkyne underwent dephosphorylation by treatment with MeMgBr in THF with Me3Si-protection untouched. The dephosphorylation followed by a transition-metal-catalyzed coupling of the resulting terminal alkyne with aryl halides was carried out in a one-pot manner to afford the desired coupling product. Selective deprotection of Me3Si-/Ph2P(O)-protected alkynes enabled facile syntheses of expanded π-systems such as cyclic phenyleneethynylenes and unsymmetrically substituted ditriazol.

  一种Ph2P(O)保护的炔烃在THF中用MeMgBr处理后发生去磷酸化，Me3Si保护未受到影响。该去磷酸化后紧接着与芳基卤化物进行的过渡金属催化偶联反应以一锅法进行，从而获得所需的偶联产物。选择性去保护Me3Si-/Ph2P(O)保护的炔烃使得扩展π系统的合成变得简便，例如环状苯乙炔和不对称取代的二三唑。