1-hept-1-ynyl-2-methyl-benzene | 64146-63-0

• 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: 1-hept-1-ynyl-2-methyl-benzene
• 英文别名: 1-(1-heptynyl)-2-methylbenzene；Benzene, 1-(1-heptynyl)-2-methyl-；1-hept-1-ynyl-2-methylbenzene
• CAS: 64146-63-0
• 化学式: C₁₄H₁₈
• 分子量: 186.297
• InChiKey: KIRBDEGMAYAQNZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 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-hept-1-ynyl-2-methyl-benzene 在 氢气 、 C₅₄H₁₀₂Mg₂N₂O₂P₄ 作用下， 以 甲苯 为溶剂， 120.0 ℃ 、500.01 kPa 条件下， 反应 24.0h， 以87.5%的产率得到
  参考文献：
  名称：

  镁钳配合物及其在炔烃催化半加氢和烯烃加氢中的应用：金属-配体合作的证据

  摘要：

  开发用于环境友好的有机转化的催化剂是一个非常活跃的研究领域。迄今为止报道的大多数催化剂都是基于过渡金属配合物。近年来，已经报道了由主族金属化合物催化的例子。在此，我们报告了一系列镁钳配合物，并通过 NMR 和 X 射线单晶衍射对其进行了表征。研究了通过芳构化/脱芳构化金属-配体合作对 H 2的可逆活化。利用所获得的配合物，在无碱条件下证明了前所未有的均相主族金属催化炔烃的半氢化和烯烃的氢化，得到Z-烯烃和烷烃分别作为产物，具有优异的收率和选择性。对照实验和 DFT 研究揭示了金属-配体合作参与氢化反应。该研究不仅为镁催化的炔烃半加氢和烯烃加氢提供了新途径，而且为主族金属配合物催化的其他化合物加氢提供了机会。

  DOI：

  10.1021/jacs.2c08491
• 作为产物：
  描述：

  1-heptynyldimethylsilane 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂ 、 potassium trimethylsilonate 、 水 作用下， 以 乙二醇二甲醚 、 乙腈 为溶剂， 反应 24.17h， 生成 1-hept-1-ynyl-2-methyl-benzene
  参考文献：
  名称：

  Cross-Coupling of Alkynylsilanols with Aryl Halides Promoted by Potassium Trimethylsilanolate

  摘要：

  The palladium-catalyzed cross-coupling of aliphatic alkynylsilanols with aryl iodides has been demonstrated with potassium trimethylsilanolate as the coupling promoter and copper(I) iodide as a cocatalyst. The cross-coupling proceeds at room temperature in good to excellent yield with a range of aryl iodides. A comparison of the reactivity of alkynylsilanols, trimethylsilylalkynes, and terminal alkynes under fluoride and fluoride-free conditions was per-formed to elucidate the role of silicon in the Sonogashira reaction.

  DOI：

  10.1021/jo0351771

文献信息

• CuI/PPh₃/PEG–Water: An Efficient Catalytic System for Cross-Coupling Reaction of Aryl Iodides and Alkynes
  作者：Gong Chen、Jianwei Xie、Jiang Weng、Xinhai Zhu、Zhanchao Zheng、Jiwen Cai、Yiqian Wan

  DOI：10.1080/00397911.2010.517363

  日期：2011.11.1

  Abstract An efficient protocol for the copper-catalyzed Sonogashira coupling of aryl iodides with terminal acetylenes in water–polyethylene glycol has been established. Both electron-rich and electron-deficient aryl iodides were arylalkynated under microwave heating or reflux in oil bath to afford good to excellent yields.

  摘要 建立了一种在水-聚乙二醇中铜催化芳基碘与末端乙炔的 Sonogashira 偶联的有效方案。在微波加热或油浴回流下，富电子和缺电子芳基碘化物均被芳基炔化，以提供良好至极好的产率。
• Regiochemical Aspects of the Platinum Oxide Catalyzed Hydrosilylation of Alkynes
  作者：Mouâd Alami、Abdallah Hamze、Olivier Provot、Jean-Daniel Brion

  DOI：10.1055/s-2007-983742

  日期：2007.7

  The platinum-catalyzed hydrosilylation of unsymmetrical substituted arylalkynes with various hydrosilanes was investigated and the reaction selectivity of various para-substituted substrates was compared with that of their corresponding ortho-substituted derivatives. We showed that heterogeneous platinum oxide is a very efficient catalyst for such hydrosilylations and that H-Si bond addition proceeds in a stereoselective cis-fashion. The regioselectivity was found to be under the control of the ortho-substituent rather than due to the nature of the platinum catalyst. Aryl­alkynes with an ortho-substituent provided predominantly to exclusively α-selectivity, regardless of the electronic nature of the substituent. The precise contributions of steric, electronic, and coordinative factors controlling the regioselectivity of the H-Si bond addition are discussed.

  对不对称取代的芳基炔与各种氢硅烷的铂催化氢硅化反应进行了研究，并比较了不同对位取代底物的反应选择性与其相应的邻位取代衍生物的反应选择性。我们展示了异相铂氧化物是一种高效的催化剂用于此类氢硅化反应，且H-Si键的加成以立体选择性的顺式方式进行。区域选择性被发现是由邻位取代基控制，而不是由铂催化剂的性质决定。带有邻位取代基的芳基炔提供了主要到完全的α-选择性，无论取代基的电子性质如何。我们还讨论了影响H-Si键加成的区域选择性的立体、电子和配位因素的精确贡献。
• Synthesis of Benzo[<i>c</i> ]silole Derivatives Bearing a Tetrasubstituted Exocyclic C=C Double Bond by Palladium-Catalyzed Domino Reactions
  作者：Patrick Wagner、Mihaela Gulea、Jean Suffert、Morgan Donnard

  DOI：10.1002/chem.201701736

  日期：2017.6.1

  The synthesis of diversely substituted 2,3‐dihydro‐benzo[c]siloles through an unprecedented palladium‐catalyzed domino sequence is reported, involving a cyclocarbopalladation of an internal silylalkyne. This reaction proceeds with complete stereoselectivity to lead to a fully substituted exocyclic C=C double bond. Notably, the overall domino sequence appears to be crucial to obtain the desired cyclic

  据报道，通过空前的钯催化的多米诺骨牌合成了多种取代的2,3-二氢-苯并[ c ]甲硅烷基，涉及内部甲硅烷基炔的环羰缩合。该反应以完全的立体选择性进行，从而导致完全取代的环外C ＝ C双键。值得注意的是，总的多米诺序列似乎对于获得所需的环状乙烯基硅烷至关重要。
• Palladium-Catalyzed Cross-Coupling of Aryl Electrophiles with Dimethylalkynylaluminum Reagents
  作者：Baomin Wang、Martine Bonin、Laurent Micouin

  DOI：10.1021/ol048741i

  日期：2004.9.1

  Alkynyldimethylaluminum reagents are easily available from terminal akynes and trimethylaluminum via a triethylamine-catalyzed metalation. These compounds can react with various aromatic and heterocyclic halides in the presence of palladium in a fast and efficient way. This catalyzed cross-coupling reaction provides a simple entry to numerous internal alkynes, using a readily available, inexpensive, and nontoxic metalating agent.
• Synthesis, characterization of palladium hydroxysalen complex and its application in the coupling reaction of arylboronic acids: Mizoroki–Heck type reaction and decarboxylative couplings
  作者：Yumi Heo、Yi Young Kang、Thiruvengadam Palani、Junseong Lee、Sunwoo Lee

  DOI：10.1016/j.inoche.2012.05.013

  日期：2012.9

  (Salen-OH)Pd (1, salen-OH=N,N'-bis(3,5-di-hydroxysalicylidene)-ethylenediamine) was prepared by a simple one step reaction and fully characterized by H-1 and C-13 NMR, IR spectroscopy, and X-ray crystallography. This palladium complex showed good activities as a catalyst in the Mizoroki-Heck-type reaction and the decarboxylative coupling reaction. In the Mizoroki-Heck type reaction, arylboronic acids and alkenes were reacted at 90 degrees C for 3 h in the presence of 2.0 mol% of the palladium complex 1 and AgOAc to give the desired coupled product in good yields. In the decarboxylative coupling reactions, the desired coupled products were obtained in good yields when 0.5 mol% of the palladium complex was employed at room temperature. (C) 2012 Elsevier B.V. All rights reserved.