1-(but-3-yn-1-yl)-2-methylbenzene | 6502-18-7

• 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-(but-3-yn-1-yl)-2-methylbenzene
• 英文别名: 1-but-3-ynyl-2-methylbenzene
• CAS: 6502-18-7
• 化学式: C₁₁H₁₂
• 分子量: 144.216
• InChiKey: DXUJGWXHZOSBKG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  11
• 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：

  1-(but-3-yn-1-yl)-2-methylbenzene 在 吡啶 、 copper diacetate 、 potassium tert-butylate 作用下， 以 叔丁醇 、 苯 为溶剂， 反应 24.0h， 生成 1,8-Di-o-tolyl-octa-1,3,5,7-tetraen
  参考文献：
  名称：

  Hubert,A.J.; Anciaux,A.J., Bulletin des Societes Chimiques Belges, 1968, vol. 77, p. 513 - 520

  摘要：

  DOI：
• 作为产物：
  描述：

  1-(o-tolyl)but-3-yn-1-ol 在 三乙基硅烷 、 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以52%的产率得到1-(but-3-yn-1-yl)-2-methylbenzene
  参考文献：
  名称：

  Superoxide mediated isomerization of 4-aryl-but-1-ynes to 1-aryl-1,3-butadienes

  摘要：

  A new role of superoxide ion in the isomerization of homobenzylic acetylenes leading to 1-aryl-1,3-butadienes is reported. The unconventional reagent 1(02 is found to be superior in performing this kind of isomerization over other the commonly used bases. For substrates containing arene moiety and triple bond connected through more than two methylene groups, and for propargylcyclohexanol the reagent selectively effected migration of the triple bond. Reactivity of 1(02 towards the substrates having disubstitution at benzylic position varied depending on the nature of the substitution, alkyl-substitution lead to isomerization to give mixture of allene (an intermediate in the isomerization of acetylene to 1,3-butadiene) and triple bond migration product; whereas phenyl-substituted compound gave 1,3-diene. The utility of the methodology was demonstrated through a Diels-Alder reaction of one of the dienes obtained by the isomerization with suitable dienophiles. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.07.075

文献信息

• Enantioselective Construction of Axially Chiral Amino Sulfide Vinyl Arenes by Chiral Sulfide‐Catalyzed Electrophilic Carbothiolation of Alkynes
  作者：Yaoyu Liang、Jieying Ji、Xiaoyan Zhang、Quanbin Jiang、Jie Luo、Xiaodan Zhao

  DOI：10.1002/anie.201915470

  日期：2020.3.16

  The enantioselective construction of axially chiral compounds by electrophilic carbothiolation of alkynes is disclosed for the first time. This enantioselective transformation is enabled by the use of a Ts-protected bifunctional sulfide catalyst and Ms-protected ortho-alkynylaryl amines (Ts=tosyl; Ms=mesyl). Both electrophilic arylthiolating and electrophilic trifluoromethylthiolating reagents are

  首次公开了通过炔的亲电碳硫基化对轴向手性化合物的对映选择性结构。通过使用Ts保护的双官能硫化物催化剂和Ms保护的邻炔基芳基胺（Ts ＝甲苯磺酰基； Ms ＝甲磺酰基），可以实现这种对映选择性转化。亲电芳基硫醇化试剂和亲电三氟甲基硫醇化试剂均适用于该反应。轴向手性乙烯基-芳基氨基硫化物的所得产物可以容易地转化为联芳基氨基硫化物，联芳基氨基亚砜，联芳基胺，乙烯基芳基胺和其他有价值的双官能化化合物。
• Metal‐Free Synthesis of Selenodihydronaphthalenes by Selenoxide‐Mediated Electrophilic Cyclization of Alkynes
  作者：Shaoyu An、Zhong Zhang、Pingfan Li

  DOI：10.1002/ejoc.202100423

  日期：2021.6.7

  A metal-free, one-pot selenium mediated electrophilic cyclization reaction of alkynes and triflic anhydride-activated selenoxides was realized, giving selenium containing dihydronaphthalene products, including selenium-substituted phenanthrene, dihydroquinoline, 2H-chromene, and coumarin.

  实现了炔烃和三氟甲磺酸酐活化的氧化硒的无金属、一锅硒介导的亲电环化反应，得到含硒的二氢萘产品，包括硒取代的菲、二氢喹啉、2 H-色烯和香豆素。
• Cobalt-Catalyzed Markovnikov Selective Sequential Hydrogenation/Hydrohydrazidation of Aliphatic Terminal Alkynes
  作者：Jieping Chen、Xuzhong Shen、Zhan Lu

  DOI：10.1021/jacs.0c07258

  日期：2020.8.26

  pot. A cobalt hydride species was employed as two roles for both a unique metal-catalyzed Markovnikov-type insertion of the aliphatic terminal alkynes and then metal-catalyzed hydrogen atom transfer of alkenes. This operationally simple protocol exhibits excellent functional group tolerance and step economy. The hydrazone products could be easily transferred to various valuable amine derivatives.

  在这里，我们首次报道了一种机械上独特的钴催化马尔科夫尼科夫型连续半氢化/氢酰肼的脂肪族末端炔烃。钴氢化物被用作脂肪族末端炔烃的独特金属催化马尔可夫尼科夫型插入和烯烃的金属催化氢原子转移的两种作用。这种操作简单的协议表现出出色的功能组耐受性和步骤经济性。腙产物可以很容易地转移到各种有价值的胺衍生物中。
• Highly Regioselective Sequential 1,1‐Dihydrosilylation of Terminal Aliphatic Alkynes with Primary Silanes
  作者：Zhaoyang Cheng、Shipei Xing、Jun Guo、Biao Cheng、Lan‐Fang Hu、Xing‐Hong Zhang、Zhan Lu

  DOI：10.1002/cjoc.201900079

  日期：2019.5

  aliphatic alkynes with primary silanes catalyzed by one cobalt catalyst has been developed. gem‐Bis(dihydrosilyl)alkanes containing four silicon‐hydrogen bonds are efficiently constructed in an atom‐economical manner. Tolerated substrates include simplest alkyne‐ethyne, a complicated drug derivative and various functionalized terminal aliphatic alkynes. Asymmetric approach using two catalysts is achieved

  已经开发了一种由一种钴催化剂催化的末端脂肪族炔烃与伯硅烷的区域选择性双1,1-氢化硅烷化反应。宝石含有四个硅-氢键-双（dihydrosilyl）烷烃中的原子，经济的方式有效地构成。容许的底物包括最简单的炔烃，复杂的药物衍生物和各种官能化的末端脂肪族炔烃。实现了使用两种催化剂的不对称方法，并具有极好的对映选择性，可以得到相应的手性产物。Si-H键到Si-C，Si-O和Si-F键的转变以及对映体的α-羟基硅烷的合成显示出合成效用。
• Cobalt-Catalyzed Asymmetric Synthesis of gem-Bis(silyl)alkanes by Double Hydrosilylation of Aliphatic Terminal Alkynes
  作者：Jun Guo、Hongliang Wang、Shipei Xing、Xin Hong、Zhan Lu

  DOI：10.1016/j.chempr.2019.02.001

  日期：2019.4

  value in asymmetric synthesis, functional materials, and medicinal chemistry. Compared with single-silyl compounds, bis(silyl) ones are understudied because of the lack of the efficient synthetic protocols. The development of efficient synthetic approaches to access bis(silyl) compounds is highly desirable for studying their basic properties and potential utilities. Here, a cobalt-catalyzed sequential

  手性有机硅烷在不对称合成，功能材料和药物化学中具有重要价值。与单甲硅烷基化合物相比，双（甲硅烷基）化合物由于缺乏有效的合成方案而被研究不足。为了研究双（甲硅烷基）化合物的基本性质和潜在用途，迫切需要开发有效的合成方法。在此，开发了脂族炔烃的钴催化的顺序双氢化硅烷化反应，以合成高度对映体富集的宝石-双（甲硅烷基）烷烃。该协议使用简单的脂肪族炔烃和硅烷来构建有价值的手性宝石-双（甲硅烷基）烷烃。进行了控制实验，同位素标记实验，动力学研究和密度泛函理论计算，以阐明反应机理。宝石-双（甲硅烷基）烷烃的合成多功能性通过手性有机硅烷醇，α-羟基硅烷的合成，通过选择性的C-Si键转换和炔烃的氢化硅烷化反应来构建，该手性硅烷包含相邻的C-立体中心和Si-立体中心。