3-(2-phenylethenyl)cyclopent-2-en-1-one | 303179-07-9

• 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: 3-(2-phenylethenyl)cyclopent-2-en-1-one
• CAS: 303179-07-9
• 化学式: C₁₃H₁₂O
• 分子量: 184.238
• InChiKey: CWVATHDXUCYMTG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.99
• 重原子数：
  14.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  3-(2-phenylethenyl)cyclopent-2-en-1-one 在 sodium perborate 、 水 、 copper hydroxide 、 溶剂黄146 、 (αS,α'S)-α,α'-双(叔丁基)-[2,2'-联吡啶]-6,6'-二甲醇 作用下， 以 水 为溶剂， 反应 12.0h， 生成
  参考文献：
  名称：

  Heterogeneous and homogeneous chiral Cu(ii) catalysis in water: enantioselective boron conjugate additions to dienones and dienoesters

  摘要：

  研究证明，在 Cu(II)催化水中对映选择性硼共轭物加成时，反离子的明智选择发挥了重要作用；使用 Cu(OH)2 可实现异相催化，而 Cu(OAc)2 则可实现均相催化；通过这些催化剂，环二烯酮在 1,4- 和 1,6- 加成模式之间发生了显著的区域选择性转换。

  DOI：

  10.1039/c3cc44324h

文献信息

• Basic Copper Carbonate-Catalyzed Silyl Conjugate Additions to α,β-Unsaturated Carbonyls in Water
  作者：Wei Wang、Bo-Jie Li、Zu-Feng Xiao、Feng Yan、Peng-Ren Wei、Lian-Sheng Wang、Lei Zhu

  DOI：10.1002/jccs.201700186

  日期：2018.1

  We report here the silylation of α,β‐unsaturated acceptors in water at room temperature using a copper catalyst. A broad substrate scope, including chalcone derivatives, esters, nitrile, and dienones, has been explored. In all cases, the reaction proceeded well to give the desired products in good to excellent yield.

  我们在这里报告使用铜催化剂在室温下水中α，β-不饱和受体的甲硅烷基化。已经探索了广泛的底物范围，包括查尔酮衍生物，酯，腈和二烯酮。在所有情况下，反应均进行良好，以良好至极佳的产率得到所需产物。
• NHC–Cu-Catalyzed Silyl Conjugate Additions to Acyclic and Cyclic Dienones and Dienoates. Efficient Site-, Diastereo- and Enantioselective Synthesis of Carbonyl-Containing Allylsilanes
  作者：Kang-sang Lee、Hao Wu、Fredrik Haeffner、Amir H. Hoveyda

  DOI：10.1021/om300790t

  日期：2012.11.26

  Efficient and highly diastereo- and enantioselective conjugate additions of phenyldimethylsilyl units to acyclic and cyclic dienones and dienoates are disclosed. The C–Si bond forming reactions are catalyzed by 2.0–2.5 mol % of a copper complex of a chiral monodentate N-heterocyclic carbene; the requisite reagent, PhMe2Si–B(pin), is commercially available or can be easily prepared. Transformations

  公开了苯基二甲基甲硅烷基单元向无环和环状二烯酮和二烯酸酯的有效和高度非对映选择性和对映选择性共轭加成。C-Si 键形成反应由 2.0-2.5 mol% 的手性单齿 N-杂环卡宾的铜配合物催化；必需的试剂 PhMe 2 Si–B(pin) 可在市场上买到或很容易制备。转化以高达 98% 的产率和 >99:1 的对映体比例生成烯丙基硅烷，并以完全的 1,4-选择性进行，除非二烯酮或二烯酸酯带有与羰基共轭的三取代烯烃；在后一种情况下，只能获得 1,6-加成产物，Z选择性高达 >98% 。
• Direct Catalytic Asymmetric Doubly Vinylogous Michael Addition of α,β-Unsaturated γ-Butyrolactams to Dienones
  作者：Xiaodong Gu、Tingting Guo、Yuanyuan Dai、Allegra Franchino、Jie Fei、Chuncheng Zou、Darren J. Dixon、Jinxing Ye

  DOI：10.1002/anie.201504276

  日期：2015.8.24

  An asymmetric doubly vinylogous Michael addition (DVMA) of α,β‐unsaturated γ‐butyrolactams to sterically congested β‐substituted cyclic dienones with high site‐, diastereo‐, and enantioselectivity has been achieved. An unprecedented DVMA/vinylogous Michael addition/isomerization cascade reaction affords chiral fused tricyclic γ‐lactams with four newly formed stereocenters.

  已实现了对位，非对映和对映异构体选择性高的α，β-不饱和γ-丁内酰胺向空间拥挤的β-取代的环状二烯的不对称双乙烯基迈克尔加成反应（DVMA）。前所未有的DVMA / vinyllogous Michael加成/异构化级联反应提供了具有四个新形成的立体中心的手性稠合三环γ-内酰胺。
• An Insoluble Copper(II) Acetylacetonate–Chiral Bipyridine Complex that Catalyzes Asymmetric Silyl Conjugate Addition in Water
  作者：Taku Kitanosono、Lei Zhu、Chang Liu、Pengyu Xu、Shu̅ Kobayashi

  DOI：10.1021/jacs.5b11418

  日期：2015.12.16

  Acicular purplish crystals were obtained from Cu(acac)(2) and a chiral bipyridine ligand. Although the crystals were not soluble, they nevertheless catalyzed asymmetric silyl conjugate addition of lip ophilic substrates in water. Indeed, the reactions proceeded efficiently only in water; they did not proceed well either in organic solvents or in mixed water/organic solvents in which the catalyst/substrates were soluble. This is in pronounced contrast to conventional organic reactions wherein the catalyst/substrates tend to be in solution. Several advantages of the chiral Cu(II) catalysis in water over previously reported catalyst systems have been demonstrated. Water is expected to play a prominent role in constructing and stabilizing sterically confined transition states and accelerating subsequent protonation to achieve high yields and enantioselectivities.