2-(3-methylene-cyclopentyl)-[1,3]dithiane | 142981-46-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二噻烷
• 英文名称: 2-(3-methylene-cyclopentyl)-[1,3]dithiane
• 英文别名: 2-(3-Methylidenecyclopentyl)-1,3-dithiane
• CAS: 142981-46-2
• 化学式: C₁₀H₁₆S₂
• 分子量: 200.369
• InChiKey: MYIIQAYFFGWPKT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  硝基乙烯 、 2-(3-methylene-cyclopentyl)-[1,3]dithiane 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以49%的产率得到2-(3-methylene-cyclopentyl)-2-(2-nitro-ethyl)-[1,3]dithiane
  参考文献：
  名称：

  新型桥头取代双环[3.2.1]辛烷-2,4-二酮的高效合成

  摘要：

  我们报告了桥头取代双环 [3.2.1] 辛烷-2,4-二酮的有效合成。它们构建的关键步骤是腈氧化物和烯烃之间的高效分子内 [3+2] 环加成。所得二氢异恶唑的还原性环裂解提供了所需的桥头取代双环[3.2.1]辛烷-2,4-二酮。

  DOI：

  10.1055/s-0030-1258499
• 作为产物：
  描述：

  (三甲基硅基)甲基氯化镁 、 3-[1,3]dithian-2-yl-cyclopentanone 在 potassium hydride 作用下， 生成 2-(3-methylene-cyclopentyl)-[1,3]dithiane
  参考文献：
  名称：

  Chelation Assistance in the Activation of Csp3-S Bonds in Nickel-Catalyzed Cross-Coupling Reactions

  摘要：

  An unprecedented chelation approach to activate C(sp)3-S bonds in nickel-catalyzed cross-coupling reactions is described. Our theme was based on the formation of a chelation complex which results in the enhancement of the reactivity of aliphatic carbon-sulfur bonds. When two dithioacetal functionalities are located in close proximity, selective olefination of one of these two dithioacetal groups can thus be achieved conveniently. Depending on the relative positions of the newly formed double bond and the remaining dithioacetal group, tandem olefination occurs to give the corresponding 1,5-bis-silyl-substituted pentadienes. Various neighboring heteroatom substituents (OR, OH, NR(2) as well as SR groups) can facilitate the olefination of a dithioacetal group. Poly(thioether) linkage afforded the corresponding degradation products via a B-sulfur elimination process. 1,3-Dimercapto- and 1,3-dithiolatopropanes furnish the cyclopropane formation under nickel-catalyzed reaction conditions. The reaction of a dihydrothiopyran with MeMgI in the presence of the nickel catalyst proceeds via a sulfur-coordinated ir-allyl complex, which can further activate the CS bond to give vinylcyclopropane.

  DOI：

  10.1021/ja00099a009

文献信息

• A chelation approach toward activation of Csp3-S bonds. Nickel-catalyzed selective cross coupling of bisdithioacetals with Grignard reagents
  作者：Ken Tsung Wong、Tien Yau Luh

  DOI：10.1021/ja00044a060

  日期：1992.8
• Chelation Assistance in the Activation of Csp3-S Bonds in Nickel-Catalyzed Cross-Coupling Reactions
  作者：Ken-Tsung Wong、Tien-Min Yuan、Maw Cherng Wang、Hsiao-Hsian Tung、Tien-Yau Luh

  DOI：10.1021/ja00099a009

  日期：1994.10

  An unprecedented chelation approach to activate C(sp)3-S bonds in nickel-catalyzed cross-coupling reactions is described. Our theme was based on the formation of a chelation complex which results in the enhancement of the reactivity of aliphatic carbon-sulfur bonds. When two dithioacetal functionalities are located in close proximity, selective olefination of one of these two dithioacetal groups can thus be achieved conveniently. Depending on the relative positions of the newly formed double bond and the remaining dithioacetal group, tandem olefination occurs to give the corresponding 1,5-bis-silyl-substituted pentadienes. Various neighboring heteroatom substituents (OR, OH, NR(2) as well as SR groups) can facilitate the olefination of a dithioacetal group. Poly(thioether) linkage afforded the corresponding degradation products via a B-sulfur elimination process. 1,3-Dimercapto- and 1,3-dithiolatopropanes furnish the cyclopropane formation under nickel-catalyzed reaction conditions. The reaction of a dihydrothiopyran with MeMgI in the presence of the nickel catalyst proceeds via a sulfur-coordinated ir-allyl complex, which can further activate the CS bond to give vinylcyclopropane.
• Efficient Synthesis of Novel Bridgehead-Substituted Bicyclo[3.2.1]octane-2,4-diones
  作者：Sebastian Wendeborn、Hannes Nussbaumer、Jürgen Schaetzer、Tammo Winkler

  DOI：10.1055/s-0030-1258499

  日期：2010.8

  construction is a highly efficient intramolecular [3+2] cycloaddition between a nitrile oxide and an olefin. The reductive ring cleavage of the resulting dihydroisoxazole provides the desired bridgehead-substituted bicyclo[3.2.1]octane-2,4-diones.

  我们报告了桥头取代双环 [3.2.1] 辛烷-2,4-二酮的有效合成。它们构建的关键步骤是腈氧化物和烯烃之间的高效分子内 [3+2] 环加成。所得二氢异恶唑的还原性环裂解提供了所需的桥头取代双环[3.2.1]辛烷-2,4-二酮。