1-乙酰基-2-(2-丙烯基)环己烷

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 1-乙酰基-2-(2-丙烯基)环己烷
• 英文名称: trans-1-Acetyl-2-(2-propenyl)cyclohexane
• 英文别名: trans-1-(2-allyl-cyclohexyl)-ethanone；1-[(1R,2S)-2-prop-2-enylcyclohexyl]ethanone
• 化学式: C₁₁H₁₈O
• 分子量: 166.263
• InChiKey: XUWDLBUKPBKIIH-MNOVXSKESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-乙酰基-2-(2-丙烯基)环己烷 在 盐酸羟胺 、 sodium acetate 、 palladium diacetate 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 13.33h， 生成 2,3,4,5,6,7-hexahydro-1-methyl-3aH-inden-2-one
  参考文献：
  名称：

  Access to Functionalized Bicyclo[4,3,0]nonenes via Palladium-Catalyzed Oxidative Cyclization of 2-Allylcyclohexyl Oximes

  摘要：

  A new palladium-catalyzed oxidative cyclization process leading to the functionalized bicyclo[4,3,0]nonenes is serendipitously discovered during attempts to form azaheterocycle by the amino-Heck reaction of trans-2-vinyl-clohexyl phosphinyloxime. Under the influence of Pd(dba)(2)/Et3N/1:1 N-2-O-2 (1:1, v/v) (Method A) or Pd(OAc)(2)/Et3N/O-2 (Method B), the reactions afford the substituted cis-1-hydroxyl-8-formyl-bicyclo[4,3,0]non-8(9)-enes or bicycle[4,3,0]non-1(9)-en-8-ones in varying yields with the incorporation of molecular oxygen into the structures. The 5,6-bicyclic scaffold of these products is presumably derived from tandem double intramolecular cyclization followed by the ring-opening of an aza-palladium(II) tricyclic intermediate.

  DOI：

  10.1021/jo5005422
• 作为产物：
  描述：

  乙酰基环已烯 在 sodium 、 四氯化钛 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 31.17h， 生成 1-乙酰基-2-(2-丙烯基)环己烷
  参考文献：
  名称：

  含不饱和取代环烷基的α-重氮β-酮腈的铑催化分子内环丙烷化

  摘要：

  制备了几种带有反式-2-烯丙基-、-乙烯基-或-苯基环烷基的α-重氮β-酮腈，并研究了它们的分子内环丙烷化反应。在 Rh2(OAc)4 (1 mol%) 作为催化剂存在下，发现烯丙基和乙烯基取代的前体在环境温度下顺利进行环丙烷化，以 47-88% 的产率提供新型三环 α-酮基环丙基腈非对映体比例范围为 79:21 至 >99:1。另一方面，含苯基类似物的催化反应没有产生任何环丙基产物，而是以定量产率提供官能化的六氢菲或四氢环戊萘衍生物。

  DOI：

  10.1055/s-0036-1588174

文献信息

• Neighboring group participation in Lewis acid-promoted [3 + 4] and [3 + 5] annulations. The stereocontrolled synthesis of tricyclic ethers
  作者：Gary A. Molander、Kimberly O. Cameron

  DOI：10.1021/jo00074a018

  日期：1993.10

  A variety of 1,4- and 1,5-keto aldehydes derived from cycloalkanes are coupled with the bis(trimethylsilyl) enol ether of methyl acetoacetate in the presence of either TMSOTf or TrSbCl6 to generate tricyclic ethers. The reactions proceed with excellent regiochemical control by a mechanism involving neighboring group participation. This mechanism involves initial formation of a bicyclic oxocarbenium ion intermediate from the keto aldehyde substrates. The geometries of selected bicyclic intermediates have been optimized using the AM1 method allowing successful prediction of the stereochemical outcomes in the cyclization in most cases. Epimerization of alpha-chiral keto aldehyde substrates does not appear to occur in these Lewis acid-promoted annulation reactions.
• Conjugate addition of allylsilanes to α,β-enones. Obtention of cyclobutyl derivatives
  作者：Roselyne Pardo、Jean-Pierre Zahra、Maurice Santelli

  DOI：10.1016/s0040-4039(01)86648-x

  日期：1979.1
• Access to Functionalized Bicyclo[4,3,0]nonenes via Palladium-Catalyzed Oxidative Cyclization of 2-Allylcyclohexyl Oximes
  作者：Jia-Liang Zhu、Sih-Ting Wu、Jr-Yun Shie

  DOI：10.1021/jo5005422

  日期：2014.4.18

  A new palladium-catalyzed oxidative cyclization process leading to the functionalized bicyclo[4,3,0]nonenes is serendipitously discovered during attempts to form azaheterocycle by the amino-Heck reaction of trans-2-vinyl-clohexyl phosphinyloxime. Under the influence of Pd(dba)(2)/Et3N/1:1 N-2-O-2 (1:1, v/v) (Method A) or Pd(OAc)(2)/Et3N/O-2 (Method B), the reactions afford the substituted cis-1-hydroxyl-8-formyl-bicyclo[4,3,0]non-8(9)-enes or bicycle[4,3,0]non-1(9)-en-8-ones in varying yields with the incorporation of molecular oxygen into the structures. The 5,6-bicyclic scaffold of these products is presumably derived from tandem double intramolecular cyclization followed by the ring-opening of an aza-palladium(II) tricyclic intermediate.
• Rhodium-Catalyzed Intramolecular Cyclopropanation of α-Diazo β-Keto Nitriles Containing an Unsaturated Substituted Cycloalkyl Group
  作者：Jia-Liang Zhu、Yung-Peng Wu

  DOI：10.1055/s-0036-1588174

  日期：2017.7

  α-diazo β-keto nitriles bearing trans-2-allyl-, -vinyl-, or -phenylcycloalkyl groups were prepared and their intramolecular cyclopropanation reactions were examined. In the presence of Rh2(OAc)4 (1 mol%) as a catalyst, the allyl- and vinyl-substituted precursors were found to undergo cyclopropanation smoothly at ambient temperature to afford novel tricyclic α-keto cyclopropyl nitriles in 47–88% yields

  制备了几种带有反式-2-烯丙基-、-乙烯基-或-苯基环烷基的α-重氮β-酮腈，并研究了它们的分子内环丙烷化反应。在 Rh2(OAc)4 (1 mol%) 作为催化剂存在下，发现烯丙基和乙烯基取代的前体在环境温度下顺利进行环丙烷化，以 47-88% 的产率提供新型三环 α-酮基环丙基腈非对映体比例范围为 79:21 至 >99:1。另一方面，含苯基类似物的催化反应没有产生任何环丙基产物，而是以定量产率提供官能化的六氢菲或四氢环戊萘衍生物。