(2Z)-2-(6,6-dimethoxyhexylidene)-5,5-dimethylcyclohexan-1-one | 876050-85-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2Z)-2-(6,6-dimethoxyhexylidene)-5,5-dimethylcyclohexan-1-one
• CAS: 876050-85-0
• 化学式: C₁₆H₂₈O₃
• 分子量: 268.397
• InChiKey: JRNDFGJNZBGUOL-JYRVWZFOSA-N

物化性质

• 沸点：
  365.6±42.0 °C(Predicted)
• 密度：
  0.991±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2Z)-2-(6,6-dimethoxyhexylidene)-5,5-dimethylcyclohexan-1-one 在 吡啶 、 lithium aluminium tetrahydride 、 2,6-bis(dimethylamino)pyridine 、 四氯化锡 、 溶剂黄146 作用下， 以 四氢呋喃 、 硝基甲烷 、 二氯甲烷 为溶剂， 反应 37.0h， 生成 N-[(E)-[(1S)-1-[(1R,2R)-2-methoxycyclohexyl]-3,3-dimethylcyclopentyl]methylideneamino]-4-methylbenzenesulfonamide
  参考文献：
  名称：

  Scope and Facial Selectivity of the Prins-Pinacol Synthesis of Attached Rings

  摘要：

  [GRAPHICS]Using a B-alkyl Suzuki cross-coupling as a key step, a concise and stereocontrolled synthesis of five- to eight-membered triisopropylsiloxy ethers having (2Z)-(6,6-dimethoxyhexylidene) or (2Z)-(5,5-dimethoxypentylidene) side chains was developed. Prins-pinacol reactions of these precursors promoted by SnCl4 provide bicyclic products in which 5-, 6-, or 7-membered rings are joined by a C-C single bond. Synthetically challenging attached ring systems in which both rings are chiral can be prepared in this fashion with high stereo- and enantioselectivity. Stabilizing through-space electrostatic interactions between the alpha-alkoxycarbenium ion and an axially positioned oxygen substituent are believed to play a significant role in organizing the transition structure of the Prins cyclization.

  DOI：

  10.1021/jo0522862
• 作为产物：
  描述：

  5,5-dimethoxypent-1-ene 在 1,1'-双(二苯膦基)二茂铁二氯化钯(II)二氯甲烷复合物 2,4,6-三甲基吡啶 、 sodium hydroxide 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 9.0h， 生成 (2Z)-2-(6,6-dimethoxyhexylidene)-5,5-dimethylcyclohexan-1-one
  参考文献：
  名称：

  Scope and Facial Selectivity of the Prins-Pinacol Synthesis of Attached Rings

  摘要：

  [GRAPHICS]Using a B-alkyl Suzuki cross-coupling as a key step, a concise and stereocontrolled synthesis of five- to eight-membered triisopropylsiloxy ethers having (2Z)-(6,6-dimethoxyhexylidene) or (2Z)-(5,5-dimethoxypentylidene) side chains was developed. Prins-pinacol reactions of these precursors promoted by SnCl4 provide bicyclic products in which 5-, 6-, or 7-membered rings are joined by a C-C single bond. Synthetically challenging attached ring systems in which both rings are chiral can be prepared in this fashion with high stereo- and enantioselectivity. Stabilizing through-space electrostatic interactions between the alpha-alkoxycarbenium ion and an axially positioned oxygen substituent are believed to play a significant role in organizing the transition structure of the Prins cyclization.

  DOI：

  10.1021/jo0522862

文献信息

• Scope and Facial Selectivity of the Prins-Pinacol Synthesis of Attached Rings
  作者：Larry E. Overman、Emile J. Velthuisen

  DOI：10.1021/jo0522862

  日期：2006.2.1

  [GRAPHICS]Using a B-alkyl Suzuki cross-coupling as a key step, a concise and stereocontrolled synthesis of five- to eight-membered triisopropylsiloxy ethers having (2Z)-(6,6-dimethoxyhexylidene) or (2Z)-(5,5-dimethoxypentylidene) side chains was developed. Prins-pinacol reactions of these precursors promoted by SnCl4 provide bicyclic products in which 5-, 6-, or 7-membered rings are joined by a C-C single bond. Synthetically challenging attached ring systems in which both rings are chiral can be prepared in this fashion with high stereo- and enantioselectivity. Stabilizing through-space electrostatic interactions between the alpha-alkoxycarbenium ion and an axially positioned oxygen substituent are believed to play a significant role in organizing the transition structure of the Prins cyclization.