m-trifluoromethylphenyl allene | 70090-81-2

• 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: m-trifluoromethylphenyl allene
• 英文别名: 1-Propadienyl-3-(trifluoromethyl)benzene
• CAS: 70090-81-2
• 化学式: C₁₀H₇F₃
• 分子量: 184.161
• InChiKey: UYLMOFGWXIFXRV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  m-trifluoromethylphenyl allene 、 联硼酸频那醇酯 在 tris-(dibenzylideneacetone)dipalladium(0) 作用下， 以 甲苯 为溶剂， 以52%的产率得到(S)-4,4,5,5-tetramethyl-2-(1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-(3-(trifluoromethyl)phenyl)prop-2-en-2-yl)-1,3,2-dioxaborolane
  参考文献：
  名称：

  Development, Mechanism, and Scope of the Palladium-Catalyzed Enantioselective Allene Diboration

  摘要：

  In the presence of a chiral phosphoramidite ligand, the palladium-catalyzed diboration of allenes can be executed with high enantioselectivity. This reaction provides high levels of selectivity with a range of aromatic and aliphatic allene substrates. Isotopic-labeling experiments, stereodifferentiating reactions, kinetic analysis, and computational experiments suggest that the catalytic cycle proceeds by a mechanism involving rate-determining oxidative addition of the diboron to Pd followed by transfer of both boron groups to the unsaturated substrate. This transfer reaction most likely occurs by coordination and insertion of the more accessible terminal alkene of the allene substrate, by a mechanism that directly provides the eta(3) pi-allyl complex in a stereospecific, concerted fashion.

  DOI：

  10.1021/ja070572k
• 作为产物：
  描述：

  1-氯甲基-3-三氟甲基苯 在 sodium hydride 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 6.17h， 生成 m-trifluoromethylphenyl allene
  参考文献：
  名称：

  Photochemical and thermal hydrations of aromatic allenes. Evidence for allyl and vinyl cation intermediates

  摘要：

  DOI：

  10.1021/jo00183a005

文献信息

• Gold(I)-Catalyzed Rearrangement of Propargyl Benzyl Ethers: A Practical Method for the Generation and in Situ Transformation of Substituted Allenes
  作者：Benoit Bolte、Yann Odabachian、Fabien Gagosz

  DOI：10.1021/ja1020469

  日期：2010.6.2

  of benzyl propargyl ethers react with a gold(I) catalyst to furnish variously substituted allenes via a 1,5-hydride shift/fragmentation sequence. This transformation is rapid and practical. It can be performed under very mild conditions (room temperature or 60 degrees C) using terminal as well as substituted alkyne substrates bearing a primary, secondary, or tertiary benzyl ether group. The allenes

  一系列苄基炔丙基醚与金 (I) 催化剂反应，通过 1,5-氢化物转移/断裂序列提供各种取代的丙二烯。这种转变迅速而实用。它可以在非常温和的条件下（室温或 60 摄氏度）使用带有伯、仲或叔苄基醚基团的末端和取代炔底物进行。由此形成的丙二烯可以与内部或外部亲核试剂原位反应，对应于整个还原取代过程，以产生更多官能化的化合物。
• Photoredox-Catalyzed Chlorotrifluoromethylation of Arylallenes: Synthesis of a Trifluoromethyl Building Block
  作者：Olga A. Storozhenko、Alexey A. Festa、Valeria A. Zolotareva、Victor B. Rybakov、Alexey V. Varlamov、Leonid G. Voskressensky

  DOI：10.1021/acs.orglett.2c04214

  日期：2023.1.20

  A new class of trifluoromethyl building blocks─2-trifluoromethyl allyl chlorides─have been obtained through a photoredox-catalyzed chlorotrifluoromethylation of aryl allenes. The reaction proceeded in a regio- and stereoselective manner. A trifluoromethylated analog of the flunarizine drug was synthesized.

  通过光氧化还原催化的芳基丙二烯氯三氟甲基化，获得了一类新的三氟甲基结构单元——2-三氟甲基烯丙基氯。反应以区域和立体选择性方式进行。合成了氟桂利嗪药物的三氟甲基化类似物。
• KAMPHUIS, J.;GROOTENHUIS, P. D. J.;BOSS, H. J. T., TETRAHEDRON LETT., 1983, 24, N 10, 1101-1104
  作者：KAMPHUIS, J.、GROOTENHUIS, P. D. J.、BOSS, H. J. T.

  DOI：——

  日期：——
• RAFIZADEH, K.;YATES, K., J. ORG. CHEM., 1984, 49, N 9, 1500-1506
  作者：RAFIZADEH, K.、YATES, K.

  DOI：——

  日期：——
• Development, Mechanism, and Scope of the Palladium-Catalyzed Enantioselective Allene Diboration
  作者：Heather E. Burks、Shubin Liu、James P. Morken

  DOI：10.1021/ja070572k

  日期：2007.7.1

  In the presence of a chiral phosphoramidite ligand, the palladium-catalyzed diboration of allenes can be executed with high enantioselectivity. This reaction provides high levels of selectivity with a range of aromatic and aliphatic allene substrates. Isotopic-labeling experiments, stereodifferentiating reactions, kinetic analysis, and computational experiments suggest that the catalytic cycle proceeds by a mechanism involving rate-determining oxidative addition of the diboron to Pd followed by transfer of both boron groups to the unsaturated substrate. This transfer reaction most likely occurs by coordination and insertion of the more accessible terminal alkene of the allene substrate, by a mechanism that directly provides the eta(3) pi-allyl complex in a stereospecific, concerted fashion.