dimethyl 2-(2,4-dideuterio-5-trimethylsilyl-2,3-pentadienyl)-2-(2,2-dimethoxyethyl)-1,3-propanedioate | 1187617-20-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: dimethyl 2-(2,4-dideuterio-5-trimethylsilyl-2,3-pentadienyl)-2-(2,2-dimethoxyethyl)-1,3-propanedioate
• CAS: 1187617-20-4
• 化学式: C₁₇H₃₀O₆Si
• 分子量: 360.491
• InChiKey: JNSCSGDBPRQGNC-QDRJLNDYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.77
• 重原子数：
  24.0
• 可旋转键数：
  10.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  71.06
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  dimethyl 2-(2,4-dideuterio-5-trimethylsilyl-2,3-pentadienyl)-2-(2,2-dimethoxyethyl)-1,3-propanedioate 在 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 生成 5-deuterio-4-(1-deuterioethenyl)-1,1-dicarbomethoxy-3-methoxy-4-cyclohexene 、 trans-4-deuterio-4-(1-deuterio-1,2-propadienyl)-1,1-dicarbomethoxy-3-methoxycyclopentane 、 cis-4-deuterio-4-(1-deuterio-1,2-propadienyl)-1,1-dicarbomethoxy-3-methoxycyclopentane
  参考文献：
  名称：

  Unusual Transposition of Allenic Framework in Intramolecular Cyclization of Acetal-Tethered (Allenylmethyl)silanes

  摘要：

  Treatment of acetal-tethered (allenylmethyl)silanes, which were obtained from the corresponding 3-bromo-5-silyl-1,3-pentadienes by a Pd-catalyzed reaction with an acetal-tethered malonate, with TiCl4 gave not only vinylcyclohexene derivatives via a standard S(E)2' pathway but also unusual allenylcyclopentane species via cyclization at the delta-position. Deuterium-labeling experiments revealed participation of a 1,2-hydride shift in a carbocation intermediate for the formation of the latter products.

  DOI：

  10.1021/ol901780d
• 作为产物：
  描述：

  (Z)-3-bromo-2,4-dideuterio-5-trimethylsilyl-1,3-pentadiene 、 dimethyl 2-(2,2-dimethoxyethyl)-1,3-propanedioate 在 bis(η3-allyl-μ-chloropalladium(II)) 、 sodium hydride 、 2,2'-双(二苯基磷)联苯 作用下， 以 四氢呋喃 为溶剂， 以75%的产率得到dimethyl 2-(2,4-dideuterio-5-trimethylsilyl-2,3-pentadienyl)-2-(2,2-dimethoxyethyl)-1,3-propanedioate
  参考文献：
  名称：

  Unusual Transposition of Allenic Framework in Intramolecular Cyclization of Acetal-Tethered (Allenylmethyl)silanes

  摘要：

  Treatment of acetal-tethered (allenylmethyl)silanes, which were obtained from the corresponding 3-bromo-5-silyl-1,3-pentadienes by a Pd-catalyzed reaction with an acetal-tethered malonate, with TiCl4 gave not only vinylcyclohexene derivatives via a standard S(E)2' pathway but also unusual allenylcyclopentane species via cyclization at the delta-position. Deuterium-labeling experiments revealed participation of a 1,2-hydride shift in a carbocation intermediate for the formation of the latter products.

  DOI：

  10.1021/ol901780d