1-ethynyl-1-((2-methylallyl)oxy)cyclohexane | 340013-05-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-ethynyl-1-((2-methylallyl)oxy)cyclohexane
• 英文别名: 1-ethynyl-1-(2-methyl-allyloxy)cyclohexane；1-ethynyl-1-(2-methylallyloxy)cyclohexane；1-Ethynyl-1-(2-methylprop-2-enoxy)cyclohexane
• CAS: 340013-05-0
• 化学式: C₁₂H₁₈O
• 分子量: 178.274
• InChiKey: BXZHIHXCHLTAIS-UHFFFAOYSA-N

物化性质

• 沸点：
  229.1±19.0 °C(Predicted)
• 密度：
  0.91±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-ethynyl-1-((2-methylallyl)oxy)cyclohexane 在 3-氰基吡啶 、 双氧水 、 甲基三氧化铼(VII) 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 72.0h， 以97%的产率得到2-(1-ethynyl-cyclohexyloxymethyl)-2-methyloxirane
  参考文献：
  名称：

  A comparison of electron transfer reagents in the reductive opening of epoxides: reasons for the superiority of titanocene based complexes

  摘要：

  Several commonly used electron transfer reagents were compared in their reactivity towards three epoxides. These substrates were designed to allow for a distinction between competing courses of the reaction. It was found that titanocene reagents were clearly superior due to their low Lewis acidity, high reduction tendency towards epoxides, and low reduction tendency towards the pivotal P-metal oxy radical intermediates. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(02)00697-x
• 作为产物：
  描述：

  2-(1-ethynyl-cyclohexyloxymethyl)-2-methyloxirane 在 [VCl3(thf)3] 、 锌 作用下， 以 四氢呋喃 为溶剂， 反应 14.0h， 以57%的产率得到1-ethynyl-1-((2-methylallyl)oxy)cyclohexane
  参考文献：
  名称：

  A comparison of electron transfer reagents in the reductive opening of epoxides: reasons for the superiority of titanocene based complexes

  摘要：

  Several commonly used electron transfer reagents were compared in their reactivity towards three epoxides. These substrates were designed to allow for a distinction between competing courses of the reaction. It was found that titanocene reagents were clearly superior due to their low Lewis acidity, high reduction tendency towards epoxides, and low reduction tendency towards the pivotal P-metal oxy radical intermediates. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(02)00697-x

文献信息

• Ruthenium-Catalyzed [2+2+2] Cycloaddition of 1,6-Enynes and Unactivated Alkynes: Access to Ring-Fused Cyclohexadienes
  作者：Rui Liu、Laurent Giordano、Alphonse Tenaglia

  DOI：10.1002/asia.201700642

  日期：2017.9.5

  The [2+2+2] intermolecular carbocyclization reactions between 1,6‐enynes and alkynes catalyzed by [RuCl(cod)(Cp*)] (cod=1,5‐cyclooctadiene, Cp*=pentamethylcyclopentadienyl) are reported to provide bicyclohexa‐1,3‐dienes. The presented reaction conditions are compatible with internal and terminal alkynes and the chemo‐ and regioselectivity issues are controlled by the presence of substituents at the

  据报道[RuCl（cod）（Cp *）]（cod = 1,5-环辛二烯，Cp * =五甲基环戊二烯基）催化的1,6-烯和炔之间的[2 + 2 + 2]分子间碳环化反应-1,3-二烯 提出的反应条件与内部和末端炔烃相容，化学和区域选择性问题是通过在炔烃配偶体的炔丙基碳中心存在取代基来控制的。
• Ruthenium-Catalyzed Hydroalkynylative Cyclization of 1,6-Enynes Induced by Substituent Effects
  作者：Rui Liu、Zhenjie Ni、Laurent Giordano、Alphonse Tenaglia

  DOI：10.1021/acs.orglett.6b01901

  日期：2016.8.19

  alkyne proceeds smoothly at room temperature to afford highly substituted five-membered cyclic compounds featuring a 1,5-enyne motif. Deuterium-labeling experiments showed that the key ruthenacyclopentene intermediate undergoes cleavage of metal–carbon bonds through the metal-assisted σ-bond metathesis reaction, thus leading to the formation of C(sp2)–H and C(sp3)–C(sp) bonds.

  在大体积取代的末端炔烃存在下，钌催化的1,6-烯炔环化在室温下平稳进行，从而得到具有1,5-烯炔基序的高度取代的五元环化合物。氘标记实验表明，关键的钌环戊烯中间体通过金属辅助的σ键复分解反应经历了金属-碳键的裂解，从而导致C（sp 2）-H和C（sp 3）-C（ sp）债券。
• Simple New Three-component Catalytic System for Enyne Metathesis
  作者：Lutz Ackermann、Christian Bruneau、Pierre H. Dixneuf

  DOI：10.1055/s-2001-11394

  日期：——

  A new active three-component catalytic system for enyne metathesis is reported. It is easily generated in situ by combination of [RuCl2(p-cymene)]2, 1,3-bis(mesityl)imidazolium chloride and Cs2CO3 and exhibits excellent performance for the intramolecular metathesis reaction even from highly substituted enynes.

  报告了一种新的用于烯炔偏析的活性三组分催化体系。该催化体系由 [RuCl2(p-cymene)]2、1,3-双（甲磺酰基）咪唑氯化物和 Cs2CO3 组合而成，易于在原位生成，即使在高取代烯炔的分子内元合成反应中也表现出优异的性能。
• Gansaeuer; Pierobon; Bluhm, Synthesis, 2001, # 16, p. 2500 - 2520
  作者：Gansaeuer、Pierobon、Bluhm

  DOI：——

  日期：——
• A comparison of electron transfer reagents in the reductive opening of epoxides: reasons for the superiority of titanocene based complexes
  作者：Andreas Gansäuer、Björn Rinker

  DOI：10.1016/s0040-4020(02)00697-x

  日期：2002.8

  Several commonly used electron transfer reagents were compared in their reactivity towards three epoxides. These substrates were designed to allow for a distinction between competing courses of the reaction. It was found that titanocene reagents were clearly superior due to their low Lewis acidity, high reduction tendency towards epoxides, and low reduction tendency towards the pivotal P-metal oxy radical intermediates. (C) 2002 Elsevier Science Ltd. All rights reserved.