(S)-Z-[6-(6,6-dimethoxyhexylidene)-4,4-dimethylcyclohexyloxy]triisopropylsilane | 876050-59-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (S)-Z-[6-(6,6-dimethoxyhexylidene)-4,4-dimethylcyclohexyloxy]triisopropylsilane
• 英文别名: [(1S,2Z)-2-(6,6-dimethoxyhexylidene)-4,4-dimethylcyclohexyl]oxy-tri(propan-2-yl)silane
• CAS: 876050-59-8
• 化学式: C₂₅H₅₀O₃Si
• 分子量: 426.756
• InChiKey: JLWLCOFKVOEIBQ-SINAZASISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.86
• 重原子数：
  29
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-Z-[6-(6,6-dimethoxyhexylidene)-4,4-dimethylcyclohexyloxy]triisopropylsilane 在 四氯化锡 、 溶剂黄146 作用下， 以 硝基甲烷 为溶剂， 反应 18.0h， 生成 N-[(E)-[(1S)-1-[(1S,2S)-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 吡啶 、 2,4,6-三甲基吡啶 、 sodium hydroxide 、 硼烷四氢呋喃络合物 、 2,6-bis(dimethylamino)pyridine 、 (R)-CBS 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 45.0h， 生成 (S)-Z-[6-(6,6-dimethoxyhexylidene)-4,4-dimethylcyclohexyloxy]triisopropylsilane
  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.