(3Z,4Z)-di-O-methyl-3-[(tri-n-butylstannyl)methylene]-4-[(trimethylsilyl)-methylene]cyclopentanedicarboxylate | 301823-35-8

• 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: (3Z,4Z)-di-O-methyl-3-[(tri-n-butylstannyl)methylene]-4-[(trimethylsilyl)-methylene]cyclopentanedicarboxylate
• 英文别名: dimethyl (3Z,4Z)-3-(tributylstannylmethylidene)-4-(trimethylsilylmethylidene)cyclopentane-1,1-dicarboxylate
• CAS: 301823-35-8
• 化学式: C₂₆H₄₈O₄SiSn
• 分子量: 571.46
• InChiKey: VVNSHXUIIMTFMA-CEXPOERHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.23
• 重原子数：
  32
• 可旋转键数：
  15
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  二甲基-2.2-二(丙-2-炔基)丙二酸二乙酯 、 叔丁基锡烷 在 tris(dibenzylideneacetone)dipalladium (0) 作用下， 以 苯 为溶剂， 以71%的产率得到(3Z,4Z)-di-O-methyl-3-[(tri-n-butylstannyl)methylene]-4-[(trimethylsilyl)-methylene]cyclopentanedicarboxylate
  参考文献：
  名称：

  Axial Chirality in 1,4-Disubstituted (ZZ)-1,3-Dienes. Surprisingly Low Energies of Activation for the Enantiomerization in Synthetically Useful Fluxional Molecules

  摘要：

  Trialkylsilyltrialkylstannes (R3Si-SnR'(3)) add to 1,6-diynes in the presence of Pd(0) and trispentaflurophenylphosphine to give 1,2-dialkylidenecyclopentanes with terminal silicon and tin substituents. The (ZZ)-geometry of these s-cis-1,3-dienes, resulting from the organometallic reaction mechanisms involved, forces the silicon and tin groups to be nonplanar, thus making the molecules axially chiral. There is rapid equilibration between the two helical forms at room-temperature irrespective of the size of the Si and Sn substituents. However, the two forms can be observed by H-1, C-13, and Sn-119 NMR spectroscopy at low temperature. The rates of enantiomerization, which depend on the Si and Sn substituents, and the substitution pattern of the cylopentane ring can be studied by dynamic NMR spectroscopy using line shape analysis. The surprisingly low energies of activation (DeltaG(double dagger) = 52-57 kJ mol(-1)) for even the bulky Si and Sn derivatives may be attributed to a widening of the exo-cyclic bond-angles of the diene carbons.

  DOI：

  10.1021/ja035136m

文献信息

• First Demonstration of Helical Chirality in 1,4-Disubstituted (<i>Z,Z</i>)-1,3-Dienes:  R₃Si−SnR‘₃-Mediated Cyclization of 1,6-Diynes
  作者：Sandra Gréau、Branko Radetich、T. V. RajanBabu

  DOI：10.1021/ja0015500

  日期：2000.9.1
• Axial Chirality in 1,4-Disubstituted (<i>ZZ</i>)-1,3-Dienes. Surprisingly Low Energies of Activation for the Enantiomerization in Synthetically Useful Fluxional Molecules
  作者：Sandra Warren、Albert Chow、Gideon Fraenkel、T. V. RajanBabu

  DOI：10.1021/ja035136m

  日期：2003.12.1

  Trialkylsilyltrialkylstannes (R3Si-SnR'(3)) add to 1,6-diynes in the presence of Pd(0) and trispentaflurophenylphosphine to give 1,2-dialkylidenecyclopentanes with terminal silicon and tin substituents. The (ZZ)-geometry of these s-cis-1,3-dienes, resulting from the organometallic reaction mechanisms involved, forces the silicon and tin groups to be nonplanar, thus making the molecules axially chiral. There is rapid equilibration between the two helical forms at room-temperature irrespective of the size of the Si and Sn substituents. However, the two forms can be observed by H-1, C-13, and Sn-119 NMR spectroscopy at low temperature. The rates of enantiomerization, which depend on the Si and Sn substituents, and the substitution pattern of the cylopentane ring can be studied by dynamic NMR spectroscopy using line shape analysis. The surprisingly low energies of activation (DeltaG(double dagger) = 52-57 kJ mol(-1)) for even the bulky Si and Sn derivatives may be attributed to a widening of the exo-cyclic bond-angles of the diene carbons.