6-methylidenespiro[1,2,3a,4,5,6a-hexahydropentalene-3,2'-1,3-dithiolane] | 142981-43-9

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫代缩醛
• 英文名称: 6-methylidenespiro[1,2,3a,4,5,6a-hexahydropentalene-3,2'-1,3-dithiolane]
• CAS: 142981-43-9
• 化学式: C₁₁H₁₆S₂
• 分子量: 212.38
• InChiKey: SAIUKKLVGYMYNM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.54
• 重原子数：
  13.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  在 三氟化硼乙醚 、 potassium hydride 、 mercury(II) oxide 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 26.0h， 生成 6-methylidenespiro[1,2,3a,4,5,6a-hexahydropentalene-3,2'-1,3-dithiolane]
  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

• Chelation Assisted Conversion of C-S Bonds into C-C Bonds
  作者：Tien-Yau Luh

  DOI：10.1080/10426509708545523

  日期：1997.1.1

  species, one of these carbon-heteroatom bonds can be activated. This strategy has been applied for the nickel-catalyzed cross coupling reactions of certain rigid bisdithioacetals. Heteroatom substituents such as hydroxy, methoxy or amino groups also assist the alkenation of aliphatic dithioacetals; and homoallylic alcohols, ethers and amines are respectively obtained in reasonably good yields Polythioethers

  当底物包含两个以上可以与金属物种共生相互作用的近端杂原子时，这些碳-杂原子键之一可以被激活。该策略已应用于某些刚性双二硫缩醛的镍催化交叉偶联反应。杂原子取代基如羟基、甲氧基或氨基也有助于脂肪族二硫缩醛的链烯化；和高烯丙醇、醚和胺分别以相当好的收率获得。聚硫醚转化为环丙烷衍生物。
• 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