2,2-dibenzyl 1,3-dithiol | 158815-38-4

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: 2,2-dibenzyl 1,3-dithiol
• CAS: 158815-38-4
• 化学式: C₁₇H₂₀S₂
• 分子量: 288.478
• InChiKey: HWHGUJRCKFKRDB-UHFFFAOYSA-N

物化性质

• 沸点：
  420.9±45.0 °C(Predicted)
• 密度：
  1.106±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.32
• 重原子数：
  19.0
• 可旋转键数：
  6.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  0.0
• 氢给体数：
  2.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  2,2-dibenzyl 1,3-dithiol 在 bis(triphenylphosphine)nickel(II) chloride 、 甲基碘化镁 作用下， 以 苯 为溶剂， 反应 18.0h， 以81%的产率得到1,1-dibenzylcyclopropane
  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
• 作为产物：
  描述：

  在 bis(triphenylphosphine)nickel(II) chloride 、 甲基碘化镁 作用下， 以 苯 为溶剂， 反应 22.0h， 生成 2,2-dibenzyl 1,3-dithiol
  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

• Normal vs. Inverted Ordering of Reduction Potentials in [FeFe]‐Hydrogenases Biomimetics: Effect of the Dithiolate Bulk
  作者：Federica Arrigoni、Luca De Gioia、Catherine Elleouet、François Y. Pétillon、Philippe Schollhammer、Jean Talarmin、Giuseppe Zampella

  DOI：10.1002/chem.202300569

  日期：2023.7.6

  Electrochemical and DFT investigations of the redox behaviours of a series of hexacarbonyl diiron dithiolate complexes [Fe2(CO)6(μ-(SCH2)2X)] with different substitution at the bridge-head atom show that, in the same experimental conditions, the dithiolate bulk exerts a control in the ordering of reduction potentials (inverted vs. normal) and in the timing of the structural changes coupled to the electron

  对桥头原子具有不同取代度的一系列六羰基二铁二硫醇配合物 [Fe 2 (CO) 6 (μ-(SCH 2 ) 2 X)] 的氧化还原行为的电化学和 DFT 研究表明，在同一实验中在这些条件下，二硫醇块体对还原电位的排序（反转与正常）以及与电子转移耦合的结构变化的时间施加控制。
• 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.