1-methylene-2-(phenylmethyl)cyclohexane | 141536-35-8

• 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-methylene-2-(phenylmethyl)cyclohexane
• 英文别名: 2-benzyl-1-methylenecyclohexane；(2-Methylidenecyclohexyl)methylbenzene
• CAS: 141536-35-8
• 化学式: C₁₄H₁₈
• 分子量: 186.297
• InChiKey: QRXFLOMMQBYKOP-UHFFFAOYSA-N

物化性质

• 沸点：
  269.8±7.0 °C(Predicted)
• 密度：
  0.93±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• 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：

  4-戊烯-1-乙酸酯 、 1-methylene-2-(phenylmethyl)cyclohexane 在 Hoveyda-Grubbs catalyst second generation 作用下， 以 苯 为溶剂， 反应 14.0h， 以17%的产率得到4-(2-苄基环己基)乙酸丁酯
  参考文献：
  名称：

  An Efficient Protocol for the Cross-Metathesis of Sterically Demanding Olefins

  摘要：

  Cross-metathesis of a wide range of previously unreactive, sterically demanding alkenes can be achieved In fair to excellent yield using a commercially available catalyst by a facile strategy involving reversal of steric preference.

  DOI：

  10.1021/ol401194h
• 作为产物：
  描述：

  2-(o-Bromobenzyl)-1-methylenecyclohexane 在 叔丁基锂 、 甲醇 作用下， 以 乙醚 、 正庚烷 、 正戊烷 为溶剂， 以98%的产率得到1-methylene-2-(phenylmethyl)cyclohexane
  参考文献：
  名称：

  Cyclization of Aryllithiums Tethered to Methylenecycloalkanes:  Stereoselective Synthesis of 4a-Substituted cis-Hexahydrofluorenes

  摘要：

  The cyclization of an aryllithium tethered to a methylenecycloalkane, generated from 2-(o-bromobenzyl)-1-methylenecycloalkanes 1, 2, and 3 by low-temperature lithium-bromine exchange, has been found to be a kinetically slow but thermodynamically favorable process that proceeds at a convenient rate in an exclusively 5-exo fashion when solutions of the aryllithium in n-heptane-di-n-butyl ether (9:1 v/v) are warmed to 45 degreesC. The cyclization affords stereoisomerically pure cis-fused products (7 and 8) when the methylenecycloalkane is five- or six-membered but it is less stereoselective when the methylenecycloalkane is seven-membered. The ring-closure of the aryllithium derived from 2-(o-bromobenzyl)-1-methylenecyclohexane (2) provides an experimentally convenient route to stereoisomerically pure 4a-substituted cis-hexahydrofluorenes in 60-90% isolated yield.

  DOI：

  10.1021/jo020593r

文献信息

• A highly regioselective 6-endo-aryl radical cyclisation: stereocontrolled synthesis of trans-octahydroanthracenes
  作者：Sitaram Pal、Monika Mukherjee、Debi Podder、Alok K. Mukherjee、Usha Ranjan Ghatak

  DOI：10.1039/c39910001591

  日期：——

  The sterocontrolled synthesis of trans-octahydroanthracenes 3, 11 and 14 through implementation of an efficient and highly regioselective 6-endo-trig-aryl radical cyclisation of the respective 2-(o-bromobenzyl)-1-methylenecyclohexanes 2, 10 and 13, with tri-n-butyltin hydride is reported, along with a single crystal X-ray structure determination of 11.

  报告了通过实施高效且高度区域选择性的6-内环三芳基自由基环化反应，将相应的2-(邻溴苄基)-1-亚烯基环己烷2、10和13合成为反式八氢蒽3、11和14，使用了三正丁基锡氢化物，并对11进行了单晶X射线结构测定。
• Alkyl radical cyclisations of methylenecyclopropane derivatives
  作者：Christine Destabel、Jeremy D Kilburn、John Knight

  DOI：10.1016/s0040-4020(01)89429-1

  日期：1994.1

  Radical cyclisations of various methylenecyclopropane derivatives have been studied. Cyclisation of diphenylsubstituted (methylenecyclopropyl)butyl radical 10 gave the unexpected cyclohexene 5, via a series of radical rearrangements. In further studies, (methylenecyclopropyl) radicals underwent exclusive 5-exo cyclisation, while (methylenecyclopropyl)butyl radicals gave mixtures of products resulting

  已经研究了各种亚甲基环丙烷衍生物的自由基环化。diphenylsubstituted（methylenecyclopropyl）的环化丁基自由基10，得到意想不到的环己烯5，经由一系列自由基重排。在进一步的研究中，对（亚甲基环丙基）自由基进行了专门的5- exo环化反应，而（亚甲基环丙基）丁基则给出了由6- exo和7-内环化反应生成的产物的混合物。在（亚甲基环丙基）-戊基自由基的尝试环化中未检测到环化产物。
• Organolanthanide catalyzed hydrogenation and hydrosilylation of substituted methylenecycloalkanes
  作者：Gary A. Molander、Jo¨rn Winterfeld

  DOI：10.1016/s0022-328x(96)06276-6

  日期：1996.11

  This communication presents a study of the scope of the catalytic hydrogenation and hydrosilylation of chiral exomethylene-substituted cyclopentanes and cyclohexanes utilizing the organolanthanide precatalysts Cp2 LnCH(SiMe3)2 (CpC5Me5; LnSm, Yb). Both reaction types are sterically driven and lead to thecis-diastereomer as the major product. Additionally, the hydrosilylation is regiospecific, the silane

  该交流介绍了利用有机镧系元素预催化剂Cp 2 LnCH（SiMe 3）2（CpC 5 Me 5 ; LnSm，Yb）对手性异亚甲基取代的环戊烷和环己烷进行催化加氢和硅氢加成反应的范围的研究。两种反应类型都是空间驱动的，并导致以顺式-非对映异构体为主要产物。另外，氢化硅烷化是区域特异性的，硅烷仅位于双键的末端位置。
• Increased Efficiency in Cross-Metathesis Reactions of Sterically Hindered Olefins
  作者：Ian C. Stewart、Christopher J. Douglas、Robert H. Grubbs

  DOI：10.1021/ol702624n

  日期：2008.2.1

  Efficiency in olefin cross-metathesis reactions is affected upon reducing the steric bulk of N-heterocyclic carbene ligands of ruthenium-based catalysts. For the formation of disubstituted olefins containing one or more allylic substituents, the catalyst bearing N-tolyl groups is more efficient than the corresponding N-mesityl catalyst. In contrast, the formation of trisubstituted olefins is more efficient

  减少钌基催化剂的N-杂环卡宾配体的空间体积会影响烯烃的交叉复分解反应的效率。为了形成含有一个或多个烯丙基取代基的二取代烯烃，带有N-甲苯基的催化剂比相应的N-间苯二甲酰基催化剂更有效。相反，使用含N-间苯三甲的催化剂形成三取代的烯烃更有效。描述了一个解释这种二分法的假设。
• A novel sequence of radical rearrangements involving the 5-exo cyclisation of a 3-(methylenecyclopropyl)propyl radical
  作者：Christine Destabel、Jeremy D. Kilburn

  DOI：10.1039/c39920000596

  日期：——

  Radical 10, generated from the corresponding imidazolethiocarbonyl derivative 3 or the phenyl selenide 4, rearranges in a six-step process to give the cyclohexene 5, after reduction; this rearrangement sequence includes the selective 5-Exo cyclisation of a (methylenecyclopropyl)propyl radical and opening of the intermediate cyclopropylmethyl radical to give a ring-expanded product.

  由相应的咪唑硫代羰基衍生物 3 或苯基硒化物 4 生成的自由基 10 在还原后经过六步重新排列得到环己烯 5；该重新排列顺序包括（亚甲基环丙基）丙基的选择性 5-Exo 环化和中间环丙基甲基自由基的开环，从而得到环扩张产物。