Dimethyl <2-(ethylenedioxy)-4-<(trimethylsilyl)ethynyl>-7-(trimethylsilyl)-6-heptynylidene>propanedioate | 132993-07-8

• 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-(ethylenedioxy)-4-<(trimethylsilyl)ethynyl>-7-(trimethylsilyl)-6-heptynylidene>propanedioate
• 英文别名: Dimethyl 2-[[2-[5-trimethylsilyl-2-(2-trimethylsilylethynyl)pent-4-ynyl]-1,3-dioxolan-2-yl]methylidene]propanedioate
• CAS: 132993-07-8
• 化学式: C₂₂H₃₄O₆Si₂
• 分子量: 450.679
• InChiKey: DLVJIUPUMRAGEG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.16
• 重原子数：
  30
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  Dimethyl <2-(ethylenedioxy)-4-<(trimethylsilyl)ethynyl>-7-(trimethylsilyl)-6-heptynylidene>propanedioate 在 palladium diacetate potassium fluoride 、 甲酸 、 三异丙基亚磷酸酯 、 copper(II) sulfate 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 5.0h， 生成 Methyl 2-(3-ethynyl-1-oxo-5-hexynyl)-1-(methoxycarbonyl)-4-methylidenecyclopentane carboxylate
  参考文献：
  名称：

  Stereoselective access to the basic skeleton of tetracyclic diterpenes via a sequence of consecutive [3 + 2], [2 + 2 + 2], and [4 + 2] cycloaddition reactions

  摘要：

  Benzocyclobutenes 9a, 9b, 23, and 24, prepared from 1,5-hexadiyne in good yields in a sequence involving [3 + 2] annelation and [2 + 2 + 2] cycloaddition reactions, underwent an intramolecular [4 + 2] reaction to afford the basic skeleton of tetracyclic diterpenes phyllocladane and kaurane. The factors governing the stereochemistry of the Diels-Alder reaction have been elucidated. A carbonyl group at C-12 favored the kaurane stereochemistry (58:42) whereas acetal or silyl ether functions at that same position led to a highly (97:3) or totally stereoselective formation of the phyllocladane ring system.

  DOI：

  10.1021/jo00068a026
• 作为产物：
  描述：

  1,6-bis(trimethylsilyl)-1,5-hexadiyne 在 哌啶 、 正丁基锂 、 草酰氯 、 ammonium cerium(IV) nitrate 、 四甲基乙二胺 、 4 A molecular sieve 、 camphor-10-sulfonic acid 、 溶剂黄146 、 二甲基亚砜 、 甲基磺酰氯 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 、 水 、 甲苯 、 乙腈 为溶剂， 反应 56.25h， 生成 Dimethyl <2-(ethylenedioxy)-4-<(trimethylsilyl)ethynyl>-7-(trimethylsilyl)-6-heptynylidene>propanedioate
  参考文献：
  名称：

  Stereoselective access to the basic skeleton of tetracyclic diterpenes via a sequence of consecutive [3 + 2], [2 + 2 + 2], and [4 + 2] cycloaddition reactions

  摘要：

  Benzocyclobutenes 9a, 9b, 23, and 24, prepared from 1,5-hexadiyne in good yields in a sequence involving [3 + 2] annelation and [2 + 2 + 2] cycloaddition reactions, underwent an intramolecular [4 + 2] reaction to afford the basic skeleton of tetracyclic diterpenes phyllocladane and kaurane. The factors governing the stereochemistry of the Diels-Alder reaction have been elucidated. A carbonyl group at C-12 favored the kaurane stereochemistry (58:42) whereas acetal or silyl ether functions at that same position led to a highly (97:3) or totally stereoselective formation of the phyllocladane ring system.

  DOI：

  10.1021/jo00068a026

文献信息

• Stereoselective access to the basic skeleton of tetracyclic diterpenes via a sequence of consecutive [3 + 2], [2 + 2 + 2], and [4 + 2] cycloaddition reactions
  作者：Corinne Aubert、Jean Pierre Gotteland、Max Malacria

  DOI：10.1021/jo00068a026

  日期：1993.7

  Benzocyclobutenes 9a, 9b, 23, and 24, prepared from 1,5-hexadiyne in good yields in a sequence involving [3 + 2] annelation and [2 + 2 + 2] cycloaddition reactions, underwent an intramolecular [4 + 2] reaction to afford the basic skeleton of tetracyclic diterpenes phyllocladane and kaurane. The factors governing the stereochemistry of the Diels-Alder reaction have been elucidated. A carbonyl group at C-12 favored the kaurane stereochemistry (58:42) whereas acetal or silyl ether functions at that same position led to a highly (97:3) or totally stereoselective formation of the phyllocladane ring system.