(E)-1,6-bis(methanesulfonyloxy)-3-methyl-2-(triisopropylsilyloxy)-3-hexene | 290292-21-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: (E)-1,6-bis(methanesulfonyloxy)-3-methyl-2-(triisopropylsilyloxy)-3-hexene
• 英文别名: [(E)-4-methyl-6-methylsulfonyloxy-5-tri(propan-2-yl)silyloxyhex-3-enyl] methanesulfonate
• CAS: 290292-21-6
• 化学式: C₁₈H₃₈O₇S₂Si
• 分子量: 458.713
• InChiKey: CMPLREGJLQBVDW-GZTJUZNOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.84
• 重原子数：
  28.0
• 可旋转键数：
  13.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  95.97
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  (E)-1,6-bis(methanesulfonyloxy)-3-methyl-2-(triisopropylsilyloxy)-3-hexene 在 2,6-二甲基吡啶 、 18-冠醚-6 、 六氯丙酮 、 4-甲基苯磺酸吡啶 、 potassium hydride 、 双(三甲基硅烷基)氨基钾 、 sodium hydride 、 caesium carbonate 、 三苯基膦 、 potassium iodide 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 异丙醇 、 甲苯 、 乙腈 为溶剂， 反应 50.67h， 生成 4α,4aα,4bβ,8aβ,10aα-tetramethyl-1,3,4,4a,4b,5,6,8,8a,10a-decahydro-4a-methyl-4-[[tris(1-methylethyl)silyl]oxy]-2,2,7,7-phenanthrenetetracarboxylate
  参考文献：
  名称：

  Transannular Diels–Alder Studies of 14-Membered cis – trans – trans Macrocyclic Trienes Having Allylic Ether or Enone Dienophile

  摘要：

  Highly convergent, malonate alkylation based syntheses of the model macrocycles and their title investigations are reported. In the allylic ether dienophile case, a preference for tricycles with equatorial ether position was found at the transition state level. Ab initio calculations also show that the origin of this preference is not only steric but stereoelectronic as well. The enone dienophile case indicates that when the enone system is not totally twisted out of planarity by the macrocyclic environment, the Diels-Alder reaction follows the usual trend in terms of dienophile activation. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00455-5
• 作为产物：
  描述：

  (E)-1-(ethoxyethoxy)-3-methyl-6-tetrahydropyranyloxy-2-(triisopropylsilyloxy)-3-hexene 在 盐酸 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 12.5h， 生成 (E)-1,6-bis(methanesulfonyloxy)-3-methyl-2-(triisopropylsilyloxy)-3-hexene
  参考文献：
  名称：

  Transannular Diels–Alder Studies of 14-Membered cis – trans – trans Macrocyclic Trienes Having Allylic Ether or Enone Dienophile

  摘要：

  Highly convergent, malonate alkylation based syntheses of the model macrocycles and their title investigations are reported. In the allylic ether dienophile case, a preference for tricycles with equatorial ether position was found at the transition state level. Ab initio calculations also show that the origin of this preference is not only steric but stereoelectronic as well. The enone dienophile case indicates that when the enone system is not totally twisted out of planarity by the macrocyclic environment, the Diels-Alder reaction follows the usual trend in terms of dienophile activation. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00455-5