cis-tetraethyl-4-[(triethylsilyl)methyl]-5-methylcyclohexane-1,1,2,2-tetracarboxylate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: cis-tetraethyl-4-[(triethylsilyl)methyl]-5-methylcyclohexane-1,1,2,2-tetracarboxylate
• 英文别名: tetraethyl (4R,5S)-4-methyl-5-(triethylsilylmethyl)cyclohexane-1,1,2,2-tetracarboxylate
• 化学式: C₂₆H₄₆O₈Si
• 分子量: 514.732
• InChiKey: YQBPZCGJQNAFQX-WOJBJXKFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.77
• 重原子数：
  35
• 可旋转键数：
  17
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  105
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  三乙基硅烷 、 tetraethyl octa-1,7-diene-4,4,5,5-tetracarboxylate 在 <(phen)PdCH3(Et2O)>^+- 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 0.25h， 以93%的产率得到trans-tetraethyl-4-[(triethylsilyl)methyl]-5-methylcyclohexane-1,1,2,2-tetracarboxylate
  参考文献：
  名称：

  官能化的1,7-二烯的环化/氢化硅烷化以形成取代的六元碳环

  摘要：

  阳离子钯络合物（phen）的钯（ME）（OET 2）+ BAR 4 - [苯= 1,10-菲咯啉; Ar = 3,5-C 6 H 3（CF 3）2 ]催化官能化的1,7-二烯的环化/氢化硅烷化反应，以高收率和中等至良好的反选择性形成甲硅烷基化环己烷。

  DOI：

  10.1016/s0040-4039(99)00022-2

文献信息

• Cyclization/hydrosilylation of functionalized 1,7-dienes to form substituted six-membered carbocycles
  作者：Carmine N. Stengone、Ross A. Widenhoefer

  DOI：10.1016/s0040-4039(99)00022-2

  日期：1999.2

  The cationic palladium complex (phen)Pd(Me)(OEt2)+BAr4−[phen = 1,10-phenanthroline; Ar = 3,5-C6H3(CF3)2] catalyzed the cyclization/hydrosilylation of functionalized 1,7-dienes to form silylated cyclohexanes in good yield and with moderate to good trans-selectivity.

  阳离子钯络合物（phen）的钯（ME）（OET 2）+ BAR 4 - [苯= 1,10-菲咯啉; Ar = 3,5-C 6 H 3（CF 3）2 ]催化官能化的1,7-二烯的环化/氢化硅烷化反应，以高收率和中等至良好的反选择性形成甲硅烷基化环己烷。
• Cyclization/Hydrosilylation of Functionalized Dienes Catalyzed by a Cationic Palladium Phenanthroline Complex
  作者：Ross A. Widenhoefer、Carmine N. Stengone

  DOI：10.1021/jo9913006

  日期：1999.11.1

  Mixtures of(phen)PdMe2 (2a) and HBAr'(4) (3a) or (phen)PdMe(Cl) (2b) and NaBAr'(4) (3b) [phen = 1, 10-phenanthroline; Ar' = 3,5-C6H3(CF3)(2)] catalyzed the cyclization/hydrosilylation of functionalized 1,6-dienes to form silylated cyclopentanes in good yield and with excellent trans selectivity about the newly formed C-C bond (typically >50:1). A range of tertiary hydrosilanes were employed in the procedure although unhindered trialkylsilanes provided the most consistent results. The protocol tolerated a range of polar functionality including esters, ethers, amides, sulfones, and cyano groups. 4,4-Disubstitution on the diene backbone promoted cyclization, and a homoallylic ester, ketone, or ether directing group was required for efficient cyclization. The procedure tolerated dienes which possessed a single trans-substituted olefin and also tolerated allylic substitution. These substituted dienes underwent cyclization/hydrosilylation to form carbocycles resulting from transfer of the silyl group to the less hindered olefin. Mixtures of 2a and 3a also catalyzed the cyclization/hydrosilylation of functionalized 1,7-dienes to form silylated cyclohexane derivatives. Cyclization/hydrosilylation of 1,7-dienes was typically slower, less stereoselective, and more sensitive to substitution than was cyclization of 1,6-dienes.