1-(1-Methylene-but-3-enyl)-cyclohexene | 61786-17-2

• 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-(1-Methylene-but-3-enyl)-cyclohexene
• 英文别名: Cyclohexene, 1-(1-methylene-3-butenyl)-；1-penta-1,4-dien-2-ylcyclohexene
• CAS: 61786-17-2
• 化学式: C₁₁H₁₆
• 分子量: 148.248
• InChiKey: NIQPKXLTFVMITC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  1-乙炔基环己烷 、 bromozinc(1+),prop-1-ene 生成 1-(1-Methylene-but-3-enyl)-cyclohexene
  参考文献：
  名称：

  相对于t炔类化合物的有机金属络合物（M = Zn，Mg，Li）：I.碳氢化合物：HCCC（R）C（R）（R）；活性和结构选择性的影响

  摘要：

  活性有机金属化合物（例如烯丙基锌，-镁，-锂和饱和锂化合物）易于与共轭炔烃进行加成反应：HCCC（R）C（R）（R），但反应活性为当双键周围的位阻增加时，位阻降低。对于使用的每种有机金属化合物，该反应是区域选择性的：与有机锌化合物进行3,4加成，与有机锂化合物（烯丙基，丁基）进行1,2加成，并与有机镁化合物进行1,2和1,4加成。

  DOI：

  10.1016/s0022-328x(00)87262-9

文献信息

• trans-Allylstannylation of certain acetylenes catalysed by ZrCl4
  作者：Naoki Asao、Yasuhisa Matsukawa、Yoshinori Yamamoto

  DOI：10.1039/cc9960001513

  日期：——

  The trans-allylstannylation of simple acetylenes 1 is catalysed by ZrCl4 to produce the corresponding alkenylstannanes 3 (or alkenes 4 upon protonolysis of the C–Sn bond) in a regio- and stereo-selective manner.

  通过 ZrCl4 催化简单乙炔 1 的反式烯丙基锡烷化反应，以区域和立体选择性的方式生成相应的烯基锡烷 3（或 C-Sn 键质子裂解后生成的烯烃 4）。
• Allylation of Unactivated and/or Functionalized Alkynes with Allylindiums
  作者：Naoya Fujiwara、Yoshinori Yamamoto

  DOI：10.1021/jo9701041

  日期：1997.4.1
• Allyl- and Benzylindium Reagents. Carboindation of Carbon−Carbon and Carbon−Nitrogen Triple Bonds
  作者：Naoya Fujiwara、Yoshinori Yamamoto

  DOI：10.1021/jo990160x

  日期：1999.5.1

  The reaction of unactivated simple terminal alkynes 1 with allylindiums in THF proceeded smoothly to give the corresponding allylation products 2 in good to high yields. This result is in marked contrast to that of the reaction carried out in DMF, where the allylation of unactivated alkynes was very sluggish. The allylic group of the reagent was attached to the internal carbon of the triple. bond, and indium was attached to the less substituted terminal carbon, except for the case of TMS substituted acetylenes 1j and 1k in which the allyl group went to the less substituted carbon of the triple band. The reaction of unactivated simple terminal and certain internal acetylenes with benzylindium in THF proceeded smoothly to afford the corresponding benzylation products 18 in good to high yields. The benzyl group was attached to the less substituted unhindered carbon of the triple bond, and indium was attached to the more sterically congested carbon. The reaction of activated nitriles 3 with allylindiums in THF at 70 degrees C gave the corresponding allylation-enamination products 4 in high to excellent yields. This reaction provides a useful method for the synthesis of highly functionalized enamines, which are not easily available via conventional methods. The mechanisms on the above three indation reactions are discussed.
• Lewis Acid Catalyzed <i>trans</i>-Allylsilylation of Unactivated Alkynes
  作者：Eiji Yoshikawa、Vladimir Gevorgyan、Naoki Asao、Yoshinori Yamamoto

  DOI：10.1021/ja970443b

  日期：1997.7.1

  The addition of different substituted allylsilanes 2 to unactivated alkynes 1 in the presence of catalytic amounts of HfCl4 or the EtAlCl2-TMSCl catalyst system produced in high yields the silylated 1,4-dienes 3 regio- and stereoselectively. The exclusive trans manner of addition was confirmed by analysis of crude reaction mixtures by H-1 NMR and capillary GLC methods. Good agreement of relative reactivities of reaction of various allylsilanes 2a-e toward phenylacetylene (la) in the presence of HfCl4 with the relative reaction rates of 2a-e with carbenium ions supported the involvement of cationic species 11 as a reaction intermediate. The mechanisms for the HfCl4 and EtAlCl2-TMS catalyzed trans-allylsilylation of alkynes are proposed.
• Lewis Acid-Catalyzed <i>trans</i>-Carbosilylation of Simple Alkynes
  作者：Naoki Asao、Eiji Yoshikawa、Yoshinori Yamamoto

  DOI：10.1021/jo960779o

  日期：1996.1.1