(4-methylpenta-1,2-diene-1,3-diyl)dibenzene

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物
• 英文名称: (4-methylpenta-1,2-diene-1,3-diyl)dibenzene
• 化学式: C₁₈H₁₈
• 分子量: 234.341
• InChiKey: VTAHIIMWVONFBW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  2-phenyl-2-(2-pehnylethynyl)-1,3-dithiolane 在 1,2-双(二苯基膦)乙烷氯化镍 作用下， 以 四氢呋喃 、 正戊烷 、 苯 为溶剂， 反应 0.5h， 生成 (4-methylpenta-1,2-diene-1,3-diyl)dibenzene
  参考文献：
  名称：

  Umpolung of Carbon−Sulfur Bonds. Novel Synthesis of Substituted Allenes from Propargylic Dithioacetals

  摘要：

  Umpolung of the carbon-sulfur bonds can be achieved by treatment of propargylic dithioacetals 1 with organocuprates. The organocopper intermediates 3 gave the corresponding allenyl thioethers 4 upon protonolysis. When alkyl halides were used, propargylic thioethers 5 were obtained exclusively. Transmetalation of organocopper intermediates 3 with ZnBr2 followed by Pd(PPh3)(4)- catalyzed coupling with vinylic or aryl halides afforded the corresponding allenyl thioethers 4. Either 4 or 5 reacted with Grignard reagents in the presence of NiCl2(dppf) to yield the corresponding allenes 9 or 10, respectively. The overall reaction can be considered to use 1 as allene-1,3-zwitterion synthons. The relative reactivities of a propargylic ether versus a propargylic dithioacetal toward an organocopper reagent were compared. The sulfur moiety apparently has higher reactivity toward the copper reagent.

  DOI：

  10.1021/jo991032b

文献信息

• Cu(I)/<i>N,N</i>-Imine Ligand Catalyzed C(sp³)–C(sp) Coupling of Alkyl Bromides with Alkynes: Scope and Mechanistic Investigation
  作者：Swati Jain、Anmol、Ruchi Sharma、Tarak Karmakar、M. Ramu Yadav

  DOI：10.1021/acs.orglett.3c01735

  日期：2023.7.28

  We have developed an efficient Cu/N,N-bidentate imine ligand catalytic system for C(sp3)–C(sp) coupling to obtain internal alkynes, di/trisubstituted allenes and strained bridged cyclic lactams in moderate to excellent yields from readily available alkyl(benzyl) bromides in one-pot transformation. Density Functional Theory (DFT) assisted mechanistic study along with control experiments support the

  我们开发了一种高效的 Cu/ N , N-二齿亚胺配体催化系统，用于 C(sp 3 )–C(sp) 偶联，以中等至优异的产率从现成的材料中获得内炔烃、二/三取代丙二烯和应变桥环内酰胺。烷基（苄基）溴的一锅转化。密度泛函理论（DFT）辅助的机理研究以及对照实验支持二炔化铜物质的参与，该铜物质与卤代烷进行单电子转移（SET）以在反应中生成自由基中间体。N , N-二齿亚胺配体在中间体铜配合物的稳定中起着至关重要的作用，并促进产物的形成。
• Novel Coupling Reactions of Dithioacetals with Organocuprate Reagents. Propargylic Dithioacetal as an Allene−1,3-Zwitterion Synthon
  作者：Hsian-Rong Tseng、Tien-Yau Luh

  DOI：10.1021/jo970700v

  日期：1997.7.1
• Umpolung of Carbon−Sulfur Bonds. Novel Synthesis of Substituted Allenes from Propargylic Dithioacetals
  作者：Hsian-Rong Tseng、Chin-Fa Lee、Lian-Ming Yang、Tien-Yau Luh

  DOI：10.1021/jo991032b

  日期：1999.11.1

  Umpolung of the carbon-sulfur bonds can be achieved by treatment of propargylic dithioacetals 1 with organocuprates. The organocopper intermediates 3 gave the corresponding allenyl thioethers 4 upon protonolysis. When alkyl halides were used, propargylic thioethers 5 were obtained exclusively. Transmetalation of organocopper intermediates 3 with ZnBr2 followed by Pd(PPh3)(4)- catalyzed coupling with vinylic or aryl halides afforded the corresponding allenyl thioethers 4. Either 4 or 5 reacted with Grignard reagents in the presence of NiCl2(dppf) to yield the corresponding allenes 9 or 10, respectively. The overall reaction can be considered to use 1 as allene-1,3-zwitterion synthons. The relative reactivities of a propargylic ether versus a propargylic dithioacetal toward an organocopper reagent were compared. The sulfur moiety apparently has higher reactivity toward the copper reagent.