1,2-dimethylene-3,4-diphenylcyclobutane | 101735-29-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,2-dimethylene-3,4-diphenylcyclobutane
• 英文别名: 1,2-diphenyl-3,4-dimethylenecyclobutane；1,2-Diphenyl-dimethylencyclobutan；(2,3-Dimethylidene-4-phenylcyclobutyl)benzene
• CAS: 101735-29-9
• 化学式: C₁₈H₁₆
• 分子量: 232.325
• InChiKey: ALJAYFKPBJFAHP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.11
• 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：

  丙-1,2-二烯基苯 在 [Cp*Ru(NCMe)₂(PPh₃)][PF₆] 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 6.0h， 以44%的产率得到1,2-dimethylene-3,4-diphenylcyclobutane
  参考文献：
  名称：

  An Opened Route to 1,3-Dimethylenecyclobutanes via Sequential Ruthenium-Catalyzed [2 + 2] Cycloaddition of Allenyl Boronate and Palladium Suzuki Coupling

  摘要：

  The regioselective head-to-head [2 + 2] cyclodimerization of allenyl boronate catalyzed by the ruthenium catalyst [Cp*RuCl(COD)] leads to a novel diboronated 1,3-dimethylenecyclobutane. Consecutive palladium-catalyzed C-C couplings open a route to novel disubstituted 1,3-dimethylenecyclobutane species. The X-ray crystalline structure of the phenyl-substituted 1,3-dimethylenecyclobutane is provided.

  DOI：

  10.1021/ja051930r

文献信息

• Organomagnesium-Catalyzed Isomerization of Terminal Alkynes to Allenes and Internal Alkynes
  作者：Raphaël Rochat、Koji Yamamoto、Michael J. Lopez、Haruki Nagae、Hayato Tsurugi、Kazushi Mashima

  DOI：10.1002/chem.201500179

  日期：2015.5.26

  the transformation of these terminal alkynes into allenes and further to internal alkynes under mild conditions. To the best of our knowledge, this example is the first of an organomagnesium‐catalyzed isomerization of alkynes. Notably, the reactions proceeded through temporally separated autotandem catalysis, thus allowing the isolation of the allene or internal alkyne species in good yields. Mechanistic

  通过N，N-二烷基胺亚胺配体1和二苄基镁的亚胺部分的苄基化反应合成有机镁络合物2。3-芳基-1-丙炔与2反应形成相应的四炔基络合物，在温和条件下，这些络合物可作为催化剂将这些末端炔烃转化为丙二烯，并进一步转化为内部炔烃。据我们所知，该实例是炔烃有机镁催化异构化的第一个实例。值得注意的是，反应通过暂时分离的自动串联催化进行，从而允许以高收率分离出烯丙基或内部炔烃。机理实验表明，具有催化活性的四炔基络合物由炔基镁，烯丙基镁和炔丙基镁物种的互变异构混合物组成。
• Reactivity of <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" altimg="si1.gif" overflow="scroll"><mml:mrow><mml:mo stretchy="false">[</mml:mo><mml:msup><mml:mrow><mml:mtext>Tism</mml:mtext></mml:mrow><mml:mrow><mml:msup><mml:mrow><mml:mtext>Pr</mml:mtext></mml:mrow><mml:mtext>i</mml:mtext></mml:msup><mml:mtext>Benz</mml:mtext></mml:mrow></mml:msup><mml:mo stretchy="false">]</mml:mo></mml:mrow></mml:math>MgMe towards secondary amines and terminal alkynes: Catalytic dehydrocoupling with hydrosilanes to afford Si–N and Si–C bonds
  作者：Michael Rauch、Renee C. Roberts、Gerard Parkin

  DOI：10.1016/j.ica.2019.03.015

  日期：2019.8

  The magnesium hydride and methyl compounds, [Tism(PriBenz)]MgX (X=H, Me), react with diphenylamine (Ph2NH) and pyrrolidine (C4H8NH) to afford the amide derivatives, [Tism(PriBenz)]MgNPh2 and [Tism(PriBenz)]MgNC4H8, while reactions with the terminal alkynes, PhC CH and (BuC)-C-n CH, afford the corresponding acetylide derivatives, [Tism(PriBenz)]MgC CPh and [Tism(PriBenz)]MgC CBun. The Mg-N bond of [Tism(PriBenz)]MgNR2 may be cleaved by hydrosilanes, such that [TismPriBenz]MgMe is an effective precatalyst for the dehydrocoupling of hydrosilanes and amines. For example, [Tism(PriBenz)]MgMe enables the conversion of a 1:1 mixture of Ph2SiH2 and C4H8NH at room temperature to the silazane, Ph2SiH(NC4H8).[Tism(PriBenz)]MgH and[Tism(PriBenz)]MgMe are also capable of dehydrocoupling PhC CH and PhSiH3 to form PhSiH2C CPh. In addition to dehydrocoupling of terminal alkynes, [Tism(PriBenz)]MgMe is also capable of achieving the isomerization 3-phenyl-1-propyne to phenylallene.