1-(1-methyl-2-propenyl)-1-cyclohexene | 54598-56-0

• 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-methyl-2-propenyl)-1-cyclohexene
• 英文别名: 1-(1-methyl-2-propenyl)cyclohexene；1-(1-methylprop-2-enyl)cyclohexene；1-(3-Buten-2-yl)-cyclohexen；1-(But-3-en-2-yl)cyclohex-1-ene；1-but-3-en-2-ylcyclohexene
• CAS: 54598-56-0
• 化学式: C₁₀H₁₆
• 分子量: 136.237
• InChiKey: IMNZZEQPKCOZRG-UHFFFAOYSA-N

物化性质

• 沸点：
  171.4±10.0 °C(Predicted)
• 密度：
  0.843±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 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-乙烯基环己醇 在 吡啶 、 [2-(benzyloxy)phenyl]diphenylphosphane 、 bi(allylnickel bromide) 、 Na{[1,3-(CF₃)2C₆H₃]4B} 、 三氯氧磷 作用下， 以 二氯甲烷 为溶剂， -40.0 ℃ 、101.33 kPa 条件下， 反应 23.0h， 生成 1-(1-methyl-2-propenyl)-1-cyclohexene
  参考文献：
  名称：

  Hydrovinylation of 1,3-Dienes:  A New Protocol, an Asymmetric Variation, and a Potential Solution to the Exocyclic Side Chain Stereochemistry Problem

  摘要：

  Cyclic and acyclic 1,3-dienes undergo efficient (substrate/catalyst = 72) heterodimerization with ethylene in the presence of a Ni catalyst prepared from [o-(PhCH2O)]C6H4PPh2, [(allyl)2NiBr]2, and Na+ BAr4- (Ar = 3,5-bis-trifluromethylphenyl), giving 1,2-addition products. Yields up to 99% can be realized for several 1-vinylcycloalkenes and 1-substituted 1,3-butadienes. Phospholanes with suitably placed hemilabile ligating groups and phosphoramidites derived from binaphthol are excellent ligands for an asymmetric variation of this reaction, the latter giving 99% yield and >95% ee's for selected substrates. An example of how an exocyclic chiral center can be used to install other stereo-centers in the ring (e. g., the carbon to which the side chain is attached) is also provided. These discoveries open an expeditious entry into several biologically relevant classes of compounds, especially those carrying tetrahydronaphthalene and related heterocyclic moieties.

  DOI：

  10.1021/ja0561338

文献信息

• Triarylphosphine Ligands with Hemilabile Alkoxy Groups: Ligands for Nickel(II)-Catalyzed Olefin Dimerization Reactions. Hydrovinylation of Vinylarenes, 1,3-Dienes, and Cycloisomerization of 1,6-Dienes
  作者：Souvagya Biswas、Aibin Zhang、Balaram Raya、T. V. RajanBabu

  DOI：10.1002/adsc.201400237

  日期：2014.7.7

  practical synthesis of these compounds. In sharp contrast, hydrovinylation of a variety of 1,3‐dienes is best catalyzed by nickel(II) complexes of 2‐benzyloxyphenyldiphenylphosphine, L5. The other two ligands, 2‐benzyloxymethyl‐ (L6) and 2‐benzyloxyethyldiphenylphosphine (L7) are much less effective in the HV of 1,3‐dienes. Nickel(II)‐catalyzed cycloisomerization of 1,6‐dienes into methylenecyclopentanes

  用2-苄氧基，2-苄氧基甲基或2-苄氧基乙基-苯基部分取代三苯膦中的一个苯基会产生一组简单的配体，这些配体在各种镍（II）催化的烯烃二聚反应中表现出截然不同的行为反应。配体与2-苄氧基苯基和2-苄氧基甲基苯基二苯基膦的配合物（分别为L5和L6）对乙烯基芳烃的氢乙烯基化（HV）最具活性，前者导致伯3-芳基-1-丁烯广泛异构化为共轭物2-芳基-2-丁烯即使在-55°C下也可以。但是，2-苄氧基甲基取代的配体L6该化合物的活性略低，在环境温度下可提供定量的HV初级产品定量收率，而没有异构化的痕迹，因此为这些化合物的实际合成提供了最佳选择。与之形成鲜明对比的是，2-苄氧基苯基二苯基膦L5的镍（II）配合物最好地催化了各种1,3-二烯的氢乙烯基化。其他两个配体，2-苄氧基甲基-（L6）和2-苄氧基乙基二苯基膦（L7）在1,3-二烯的HV方面效力低得多。镍（II）催化的1,6-二烯环化异构化为亚甲基环
• γ-Selective Cross-coupling of Potassium Allyltrifluoroborates with Aryl and 1-Alkenyl Bromides Catalyzed by a Pd(OAc)₂/D-<i>t</i>-BPF Complex
  作者：Yasunori Yamamoto、Shingo Takada、Norio Miyaura

  DOI：10.1246/cl.2006.704

  日期：2006.7

  Cross-coupling reactions of [RCH=CHCH2BF3]K with aryl or 1-alkenyl bromides occurred at the γ-carbon of an allylborane moiety with perfect regioselectivities (>99%) in the presence of a palladium/D-t-BPF complex and K2CO3 in refluxing THF.

  在钯/D-t-BPF 复合物和 K2CO3 的存在下，在回流四氢呋喃中，[RCH=CHCH2BF3]K 与芳基或 1-烯基溴的交叉偶联反应在烯丙基硼烷分子的 γ 碳上发生，具有完美的区域选择性（大于 99%）。
• Regio- and Stereoselective Ruthenium-Catalyzed Hydrovinylation of 1,3-Dienes:  Application to the Generation of a 20(<i>S</i>) Steroidal Side Chain
  作者：Zhengjie He、Chae S. Yi、William A. Donaldson

  DOI：10.1021/ol030031+

  日期：2003.5.1

  The addition of ethylene to 1,3-dienes and 1-vinylcycloalkenes, catalyzed by two ruthenium complexes, proceeds in a regioselective fashion to afford 3-methyl-1,4-dienes as products. For a steroidal-based 1-vinylcycloalkene, the addition is stereospecific, giving a product with a 20(S) configuration.
• Asymmetric Hydrovinylation of 1-Vinylcycloalkenes. Reagent Control of Regio- and Stereoselectivity
  作者：Jordan P. Page、T. V. RajanBabu

  DOI：10.1021/ja301640e

  日期：2012.4.18

  1-Vinylcycloalkenes undergo highly regio- and enantioselective (>98% ee) 1,4-hydrovinylation (HV) when treated with ethylene (1 aim) at room temperature in the presence of [(S,S)-2,4-bis-diphenylphosphinopentane (BDPP)]CoCl2 (0.05 equiv) and methylaluminoxane. The minor 1,2-HV products, seen only in 1-vinylcyclohexene (similar to 15%) and 1-vinylcycloheptene (2%), are formed as racemic mixtures. The corresponding Ni(II)-catalyzed HV reactions of these substrates give mostly the 1,2-adducts. Racemic 4-tert-butyl-1-vinylcyclohexene, when treated with Co[(S,S)-(BDPP)]Cl-2 and ethylene, undergoes a rare enantiodivergent reaction giving two diastereomers each in >98% cc.
• Hydrovinylation of 1,3-Dienes:  A New Protocol, an Asymmetric Variation, and a Potential Solution to the Exocyclic Side Chain Stereochemistry Problem
  作者：Aibin Zhang、T. V. RajanBabu

  DOI：10.1021/ja0561338

  日期：2006.1.1

  Cyclic and acyclic 1,3-dienes undergo efficient (substrate/catalyst = 72) heterodimerization with ethylene in the presence of a Ni catalyst prepared from [o-(PhCH2O)]C6H4PPh2, [(allyl)2NiBr]2, and Na+ BAr4- (Ar = 3,5-bis-trifluromethylphenyl), giving 1,2-addition products. Yields up to 99% can be realized for several 1-vinylcycloalkenes and 1-substituted 1,3-butadienes. Phospholanes with suitably placed hemilabile ligating groups and phosphoramidites derived from binaphthol are excellent ligands for an asymmetric variation of this reaction, the latter giving 99% yield and >95% ee's for selected substrates. An example of how an exocyclic chiral center can be used to install other stereo-centers in the ring (e. g., the carbon to which the side chain is attached) is also provided. These discoveries open an expeditious entry into several biologically relevant classes of compounds, especially those carrying tetrahydronaphthalene and related heterocyclic moieties.