(R)-4,4,4-trifluoro-3-(4-methoxyphenyl)-1-phenylbutan-1-one | 1020171-85-0

• 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: (R)-4,4,4-trifluoro-3-(4-methoxyphenyl)-1-phenylbutan-1-one
• 英文别名: (R)-beta-(4-Methoxyphenyl)-gamma,gamma,gamma-trifluorobutyrophenone；(3R)-4,4,4-trifluoro-3-(4-methoxyphenyl)-1-phenylbutan-1-one
• CAS: 1020171-85-0
• 化学式: C₁₇H₁₅F₃O₂
• 分子量: 308.3
• InChiKey: XEKFSIQAFBSKKL-OAHLLOKOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  (E)-4,4,4-trifluoro-3-(4-methoxyphenyl)-1-phenylbut-2-en-1-one 在 甲酸 、 Noyori's catalyst 、 1,5,7-三氮杂双环[4.4.0]癸-5-烯 、 三乙胺 作用下， 以 甲苯 为溶剂， 反应 72.0h， 生成 (R)-4,4,4-trifluoro-3-(4-methoxyphenyl)-1-phenylbutan-1-one
  参考文献：
  名称：

  通过离子对碱催化缺电子烯丙醇和醚的立体有择异构化

  摘要：

  已开发出一种用于烯丙醇和烯丙醚异构化的温和碱催化策略。实验和计算研究表明，当存在碱性添加剂时，不需要过渡金属催化剂。与在碱性条件下使用过渡金属的情况一样，仅由碱催化的异构化也遵循立体定向途径。该反应由限速去质子化引发。在烯丙基阴离子和碱的共轭酸之间形成紧密离子对导致手性的有效转移。通过这种机制，烯丙醇中包含的立体化学信息被转移到酮产品中。立体有择异构化也首次适用于烯丙基醚，

  DOI：

  10.1021/jacs.6b08350

文献信息

• Base-promoted isomerization of CF₃-containing allylic alcohols to the corresponding saturated ketones under metal-free conditions
  作者：Yoko Hamada、Tomoko Kawasaki-Takasuka、Takashi Yamazaki

  DOI：10.3762/bjoc.13.149

  日期：——

  the 4,4,4-trifluorobut-2-en-1-ol system under metal-free conditions to afford the corresponding saturated ketones in high to excellent chemical yields using such a convenient and easy-to-handle base as DBU at the toluene refluxing temperature, and utilization of the corresponding optically active substrates unambiguously demonstrated that this transformation proceeded in a highly stereoselective fashion

  遵循计算的期望，我们先前报道的有趣的4,4,4-三氟丁-2-yn-1-ols的1,3-质子移位已成功扩展到4,4,4-三氟丁-2-en-1在甲苯回流温度下使用方便且易于操作的碱（例如DBU），在无金属条件下使用-ol体系制得高至优异的化学收率的相应饱和酮，并明确利用了相应的光学活性底物，表明这种转变以高度立体选择性的方式进行。
• Rhodium(<scp>i</scp>)-catalyzed 1,4-conjugate arylation toward β-fluoroalkylated electron-deficient alkenes: a new entry to a construction of a tertiary carbon center possessing a fluoroalkyl group
  作者：Atsunori Morigaki、Tomoo Tanaka、Tomotsugu Miyabe、Takashi Ishihara、Tsutomu Konno

  DOI：10.1039/c2ob26708j

  日期：——

  Treatment of β-fluoroalkylated-α,β-unsaturated ketones with 1.2 equiv. of various arylboronic acids in the presence of 5 mol% of [Rh(COD)2]BF4 and 6 mol% of (S)-BINAP in toluene/H2O (v/v = 4/1) at the reflux temperature for 3 h gave the corresponding Michael adducts in high yields with over 90% enantioselectivity. Though other electron-deficient alkenes, such as vinylsulfone and vinylphosphonate, were found to be much less reactive in the rhodium-catalyzed conjugate addition with arylboronic acids, the reaction of various arylstannanes toward such electron-deficient alkenes took place very smoothly to afford the corresponding adducts in high yields.

  在甲苯/H2O（v/v = 4/1）溶液中，加入 5 摩尔的[Rh(COD)2]BF4 和 6 摩尔的(S)-BINAP，在回流温度下，用 1.2 等份的各种芳基硼酸处理δ-氟烷基化-δ,δ-不饱和酮 3 小时，可得到相应的迈克尔加合物，产率高，对映选择性超过 90%。虽然其他缺电子烯类，如乙烯基砜和乙烯基膦酸，在铑催化的芳基硼酸共轭加成反应中反应性要差得多，但各种芳基锡烷与这些缺电子烯类的反应非常顺利，能以高产率得到相应的加合物。
• One-pot relay reduction–isomerization of β-trifluoromethylated-α,β-unsaturated ketones to chiral β-trifluoromethylated saturated ketones over combined catalysts in aqueous medium
  作者：Xuelin Xia、Meng Wu、Ronghua Jin、Tanyu Cheng、Guohua Liu

  DOI：10.1039/c5gc00479a

  日期：——

  Combining Ru-functionalized silica and RuCl(PPh₃)₃ enables one-pot relay reduction-isomerizations of β-CF₃-substituted-α,β-unsaturated ketones to chiral saturated ketones.

  将Ru功能化的二氧化硅和RuCl(PPh3)3结合起来，可以实现一锅法中继还原-异构化反应，将β-CF3取代的α，β-不饱和酮转化为手性饱和酮。
• A first high enantiocontrol of an asymmetric tertiary carbon center attached with a fluoroalkyl group via Rh(I)-catalyzed conjugate addition reaction
  作者：Tsutomu Konno、Tomoo Tanaka、Tomotsugu Miyabe、Atsunori Morigaki、Takashi Ishihara

  DOI：10.1016/j.tetlet.2008.01.122

  日期：2008.3

  Treatment of fluoroalkylated electron-deficient olefins with various boronic acids in the presence of a catalytic amount of Rh(l) coordinated with (S)-BINAP in toluene/H2O at the reflux temperature for 3 h gave the corresponding conjugate addition products with high enantioselectivity in high yields. (C) 2008 Elsevier Ltd. All rights reserved.
• Base-Catalyzed Stereospecific Isomerization of Electron-Deficient Allylic Alcohols and Ethers through Ion-Pairing
  作者：Samuel Martinez-Erro、Amparo Sanz-Marco、Antonio Bermejo Gómez、Ana Vázquez-Romero、Mårten S. G. Ahlquist、Belén Martín-Matute

  DOI：10.1021/jacs.6b08350

  日期：2016.10.12

  between an allylic anion and the conjugate acid of the base results in efficient transfer of chirality. Through this mechanism, stereochemical information contained in the allylic alcohols is transferred to the ketone products. The stereospecific isomerization is also applicable for the first time to allylic ethers, yielding synthetically valuable enantioenriched (up to 97% ee) enol ethers.

  已开发出一种用于烯丙醇和烯丙醚异构化的温和碱催化策略。实验和计算研究表明，当存在碱性添加剂时，不需要过渡金属催化剂。与在碱性条件下使用过渡金属的情况一样，仅由碱催化的异构化也遵循立体定向途径。该反应由限速去质子化引发。在烯丙基阴离子和碱的共轭酸之间形成紧密离子对导致手性的有效转移。通过这种机制，烯丙醇中包含的立体化学信息被转移到酮产品中。立体有择异构化也首次适用于烯丙基醚，