3-((E)-2-phenylethenyl)cyclopentanone | 783370-36-5

• 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: 3-((E)-2-phenylethenyl)cyclopentanone
• 英文别名: (3S)-3-[(E)-2-phenylvinyl]cyclopentanone；(S,E)-3-(styryl)cyclopentan-1-one；(S)-(E)-3-(styryl)cyclopentanone；(S)-3-[(E)-2-phenylethenyl]cyclopentanone；(3S)-3-[(E)-2-phenylethenyl]cyclopentan-1-one
• CAS: 783370-36-5
• 化学式: C₁₃H₁₄O
• 分子量: 186.254
• InChiKey: ARBZJQANXYUBNI-SYTKJHMZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  2-环戊烯酮 、 反式-BETA-苯乙烯硼酸 在 potassium phosphate 、 [RhCl((S,S)^Me2dbCOT)]₂ 作用下， 以 水 、 甲苯 为溶剂， 以42%的产率得到3-((E)-2-phenylethenyl)cyclopentanone
  参考文献：
  名称：

  平面手性二苯并[a，e]环辛酸酯对铑（I）催化对映选择性的控制

  摘要：

  平面手性5,11-二取代的二苯并[ a，e ]环辛酸酯（dbCOT）已被开发为dbCOT-配体的第一个有用的手性同系物，用于不对称应用。描述了能够以克级对映体纯形式制备此类化合物的方法。在铑（I）催化的1,4和1,2芳基化反应中被评估为配体，形成了叔和四元立体异构中心，产率高，选择性高达ee > 99％  。（-）-penifulvin A的关键环化前体的催化不对称合成突出了该系统的应用背景。

  DOI：

  10.1002/chem.201704816

文献信息

• Chiral [2.2.2] Dienes as Ligands for Rh(I) in Conjugate Additions of Boronic Acids to a Wide Range of Acceptors
  作者：Christian Defieber、Jean-François Paquin、Sonia Serna、Erick M. Carreira

  DOI：10.1021/ol048240x

  日期：2004.10.1

  [reaction: see text] We document a series of investigations that led to new substituted [2.2.2]-diene ligands which display high selectivity in Rh(I)-catalyzed conjugate addition reactions to substrates not previously examined with diene ligands. Moreover, we disclose an unexpected, interesting effect that results from the introduction of a third C=C onto the ligand scaffold (cf. 1).

  [反应：见正文]我们记录了一系列研究，这些研究导致了新的取代的[2.2.2]-二烯配体，在Rh（I）催化的共轭加成反应中，对先前未用二烯配体检查的底物表现出高选择性。此外，我们公开了由于在配体支架上引入了第三个C = C而产生的出乎意料的有趣效果（参见1）。
• Room-Temperature Rhodium-Catalyzed Asymmetric 1,4-Addition of Potassium Trifluoro(organo)borates
  作者：Thomas Gendrineau、Jean-Pierre Genet、Sylvain Darses

  DOI：10.1021/ol901321r

  日期：2009.8.6

  For the first time the room-temperature rhodium-catalyzed asymmetric 1,4-addition of potassium aryltrifluoroborates to α,β-unsaturated substrates is described. Thanks to the use of a chiral diene as ligand for rhodium and triethylamine as base, to facilitate transmetalation of the boron species, high yields and enantioselectivities were generally achieved. Moreover, the use of such tetravalent boron

  首次描述了室温下铑催化的不对称1,4-芳基三氟硼酸钾向α，β-不饱和底物的加成反应。由于使用手性二烯作为铑和三乙胺作为碱的配体，为了促进硼物种的金属转移，通常获得了高收率和对映选择性。此外，与使用硼酸相比，在稳定性和易于纯化方面，使用此类四价硼物质提供了一些改进。
• Application of chiral tetrahydropentalene ligands in rhodium-catalyzed 1,4-addition of (E)-2-phenylethenyl- and (Z)-propenylboronic acids to enones
  作者：Sarah Helbig、Kirill V. Axenov、Stefan Tussetschläger、Wolfgang Frey、Sabine Laschat

  DOI：10.1016/j.tetlet.2012.04.130

  日期：2012.7

  6aR)-1 have been prepared and used as ligands in the Rh-catalyzed 1,4-addition of 1-alkenylboronic acids to cyclic enones 5. It has been discovered that the stereochemistry of the reaction was controlled by the steric properties of the aryl groups in 1 rather than their electronic nature. In the vinylation with (E)-2-phenylethenylboronic acid 5, ligands (3aR,6aR)-1 provided enantioselectivity up to 87%

  已经制备了手性四氢戊烯（3a R，6a R）-1，并用作在Rh催化的1-烯基硼酸与环状烯酮5的Rh催化的1,4-加成中的配体。已经发现，反应的立体化学是由芳基中1的空间性质而不是其电子性质控制的。在用（E）-2-苯基乙烯基硼酸5进行乙烯基化反应中，配体（3a R，6a R）-1在存在1的情况下提供高达87％ee的对映选择性，并获得高产率的乙烯基酮6（6.6mol％）。用（3a R，6a R）-1获得的所有酮产物的构型为（S）。在配体（3a R，6a R）-1存在下，Rh催化的环戊烯酮4a和（Z）-丙烯基硼酸7反应在50°C下产生（Z）-和（E）-酮8与（Z）-8是主要产物，并且两者均仅适度对映体过量。
• Sulfoxide–Alkene Hybrids: A New Class of Chiral Ligands for the Hayashi–Miyaura Reaction
  作者：Tobias Thaler、Li-Na Guo、Andreas K. Steib、Mihai Raducan、Konstantin Karaghiosoff、Peter Mayer、Paul Knochel

  DOI：10.1021/ol200841x

  日期：2011.6.17

  Sulfoxide-alkene hybrids are introduced as a new class of chiral heterodentate ligands for the Hayashi-Miyaura reaction. The synthesis of these ligands was achieved without the use of protecting groups. A chiral resolution was performed via simple column-chromatographic separation of the diastereomeric ligands. Both diastereomers proved to be excellent ligands In Rh-catalyzed 1,4-addition reactions, furnishing chiral Products with high enantloselectivities and, remarkably, opposite stereoconfigurations.
• Rhodium-catalyzed asymmetric 1,4-addition of alkenylsilanes generated by hydrosilylation of alkynes: a one-pot procedure where a rhodium/(S)-binap complex catalyzes the two successive reactions
  作者：Yusuke Otomaru、Tamio Hayashi

  DOI：10.1016/j.tetasy.2004.07.003

  日期：2004.9

  A rhodium complex [Rh((S)-binap)(MeCN)(2)]BF4 (3mol%) catalyzes successively hydrosilylation of 1-alkynes with triethoxysilane and asymmetric 1,4-addition of the resulting alkenylsilanes to cyclic alpha,beta-unsaturated ketones. This one-pot procedure gave high yield of the corresponding 1,4-addition products with over 90% enantioselectivity. (C) 2004 Elsevier Ltd. All rights reserved.