(E)-ethyl 3-methyl-5-phenylpent-2-en-4-ynoate | 308357-39-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (E)-ethyl 3-methyl-5-phenylpent-2-en-4-ynoate
• 英文别名: ethyl (E)-3-methyl-5-phenylpent-2-en-4-ynoate；trans-3-Methyl-5-phenyl-penten-2-in-4-saeure-ethylester；ethyl (2E)-3-methyl-5-phenylpent-2-en-4-ynoate
• CAS: 308357-39-3
• 化学式: C₁₄H₁₄O₂
• 分子量: 214.264
• InChiKey: GSFXWFKVPJQKHE-VAWYXSNFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-ethyl 3-methyl-5-phenylpent-2-en-4-ynoate 在 palladium diacetate 、 一氯化碘 、 三苯基膦 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 5.66h， 生成 4-methyl-6-phenyl-2H-pyran-2-one
  参考文献：
  名称：

  Discovery of a novel series of N -hydroxypyridone derivatives protecting astrocytes against hydrogen peroxide-induced toxicity via improved mitochondrial functionality

  摘要：

  Astrocytes play a key role in brain homeostasis, protecting neurons against neurotoxic stimuli such as oxidative stress. Therefore, the neuroprotective therapeutics that enhance astrocytic functionality has been regarded as a promising strategy to reduce brain damage. We previously reported that ciclopirox, a well-known antifungal N-hydroxypyridone compound, protects astrocytes from oxidative stress by enhancing mitochondrial function. Using the N-hydroxypyridone scaffold, we have synthesized a series of cytoprotective derivatives. Mitochondrial activity assay showed that N-hydroxypyridone derivatives with biphenyl group have comparable to better protective effects than ciclopirox in astrocytes exposed to H2O2. N-hydroxypyridone derivatives, especially 11g, inhibited membrane-induced deterioration of mitochondrial membrane potential and oxygen consumption rate, and significantly improved cell viability of astrocytes. The results indicate that the N-hydroxypyridone motif can provide a novel cytoprotective scaffold for astrocytes via enhancing mitochondrial functionality. (C) 2017 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2016.12.052
• 作为产物：
  描述：

  ethyl (Z)-3-methyl-5-phenylpent-2-en-4-ynoate 在 氯化二乙基铝 、 三苯基膦 作用下， 生成 (E)-ethyl 3-methyl-5-phenylpent-2-en-4-ynoate
  参考文献：
  名称：

  钯催化炔烃的高度化学和区域选择性形式[2 + 2 + 2]顺序环加成反应：众所周知的三聚反应的复兴？

  摘要：

  提出了通过钯催化的炔烃的正分子[2 + 2 + 2]顺序分子间三聚化形成苯环的高度化学和区域选择性的新概念。末端炔烃的均质化和随后的用二炔进行的[4 + 2]苯环烷基化反应以中等至良好的收率得到四取代的苯。在序列的第一步中引入两个不同的炔烃（末端和内部）可以从三个不同的无环炔基单元构建五取代的苯。在所有情况下，四取代和五取代的苯均作为单一反应产物形成，而没有任何区域或化学异构体。观察到在路易斯酸/膦组合系统存在下顺序三聚反应的显着加速。机理研究表明，在序列第一步中形成的E-烯炔的路易斯酸辅助异构化为反应性更高的Z-异构体是观察到的加速作用的原因。所提出的方法为多功能芳香族化合物提供了概念上新的，合成上有用的途径。

  DOI：

  10.1021/jo0100392

文献信息

• Chemoselective Biohydrogenation of Alkenes in the Presence of Alkynes for the Homologation of 2‐Alkynals/3‐Alkyn‐2‐ones into 4‐Alkynals/Alkynols
  作者：Danilo Colombo、Elisabetta Brenna、Francesco G. Gatti、Maria Chiara Ghezzi、Daniela Monti、Fabio Parmeggiani、Francesca Tentori

  DOI：10.1002/adsc.201900177

  日期：——

  activated alkene bonds by ene‐reductases (ERs) is completely chemoselective, because of the mechanism of the reaction. Thus, we investigated the use of ERs belonging to the Old Yellow Enzyme family for the reduction of α,β‐unsaturated aldehydes with a conjugated C≡C triple bond at the γ position. This reaction was exploited as the key step for the development of an effective homologation route to convert

  在炔烃的存在下烯烃的化学选择氢化是用传统化学方法实现的非常具有挑战性的转化。开发一种有效的方法来进行这种转化将丰富有机化学家可用的工具包，以开发有用的合成路线，并创建新的结构基序。由于反应机理，烯还原酶（ER）还原活化的烯烃键是完全化学选择性的。因此，我们研究了使用旧黄色酶家族的ER来还原在γ位上具有共轭C≡C三键的α，β-不饱和醛。
• Dramatic Acceleration of the Pd-Catalyzed [4+2] Benzannulation Reaction of Enynes and Diynes in the Presence of Lewis Acids and Bases:  Expanded Scope and New Mechanistic Insights
  作者：Marina Rubina、Matthew Conley、Vladimir Gevorgyan

  DOI：10.1021/ja060085p

  日期：2006.5.1

  nature of Lewis acid acceleration does not only lie in the isomerization of conjugated enynes but also in the direct acceleration of the [4+2] benzannulation reaction. These experimental findings, combined with the deuterium-labeling studies and DFT calculations, led to a mechanistic rationale, which (a) reasonably accounts for the observed acceleration of the reaction by Lewis acid and bases; (b) provides

  已经探索了在存在路易斯酸/膦组合或存在布朗斯台德碱的情况下钯催化的 [4+2] 苯并环化和顺序 [2+2+2] 三聚反应的显着加速。这些新的条件允许显着提高反应速率和拓宽底物范围，并显着提高反应产率，特别是对于有问题的五取代苯。发现路易斯酸加速的真正性质不仅在于共轭烯炔的异构化，而且在于[4+2]苯并环化反应的直接加速。这些实验结果，结合氘标记研究和 DFT 计算，得出了一个机械原理，(a) 合理地解释了观察到的路易斯酸和碱对反应的加速；(b) 为苯并环化机制中的闭环步骤提供了可行的替代途径；(c) 阐明氢迁移的机制；(d) 首次为苯并环化反应过程中氢迁移的显着立体选择性的起源提供了基本原理。
• Ruthenium/Halide Catalytic System for CC Bond Forming Reaction between Alkynes and Unsaturated Carbonyl Compounds
  作者：Takahiro Nishimura、Yosuke Washitake、Sakae Uemura

  DOI：10.1002/adsc.200700371

  日期：2007.12.10

  with alkyl acrylates proceeds in the presence of a catalytic amount of Ru3(CO)12 and lithium iodide to give the corresponding conjugate dienes. These two different types of catalytic carbon-carbon bond forming reactions are controlled only by the nature of halide ions, either a chloride or an iodide, with other conditions being kept almost the same.

  在双（三苯基膦）亚甲基氯化铵（[PPN] Cl）存在下的钌络合物[十二碳三钌，Ru 3（CO）12 ]催化末端炔烃向丙烯酸烷基酯的共轭加成反应，从而获得高产率的γ，δ-炔基酯。另一方面，末端炔与丙烯酸烷基酯的线性共聚反应在催化量的Ru 3（CO）12和碘化锂的存在下进行，得到相应的共轭二烯。这两种不同类型的催化碳-碳键形成反应仅受卤离子（氯离子或碘离子）的性质控制，其他条件几乎保持不变。
• Highly Enantioselective Epoxidation of α,β-Unsaturated Esters by Chiral Dioxirane
  作者：Xin-Yan Wu、Xuegong She、Yian Shi

  DOI：10.1021/ja020478y

  日期：2002.7.1

  This paper describes a highly enantioselective epoxidation of α,β-unsaturated esters using the fructose-derived ketone 2 as catalyst and Oxone as oxidant. High ee's have been obtained for a number of trans and trisubstituted substrates (82−98% ee). The results described show that it is feasible for dioxiranes to effectively epoxidize electron-deficient olefins with high ee's.

  本文描述了使用果糖衍生的酮 2 作为催化剂和 Oxone 作为氧化剂的 α,β-不饱和酯的高度对映选择性环氧化。许多反式和三取代底物 (82-98% ee) 都获得了高 ee。所描述的结果表明，二环氧乙烷有效地环氧化具有高ee值的缺电子烯烃是可行的。
• Low Coordination State Rh ^I ‐Complex as High Performance Catalyst for Asymmetric Intramolecular Cyclopropanation: Construction of <i>penta</i> ‐Substituted Cyclopropanes
  作者：Junyou Zhang、Weici Xu、Ming‐Hua Xu

  DOI：10.1002/anie.202216799

  日期：2023.3

  broad-scope rhodium (I)/chiral diene catalytic system has been developed that allows otherwise difficult-to-access penta-substituted cyclopropanes to be prepared in a highly enantioselective manner through asymmetric intramolecular cyclopropanation of rather challenging tri-substituted allylic diazoacetates. Extraordinary high performance of RhI/diene complex is showcased with low catalyst loading as little

  已开发出一种简单、广泛的铑 (I)/手性二烯催化体系，该体系允许通过相当具有挑战性的三取代烯丙基重氮乙酸酯的不对称分子内环丙烷化，以高度对映体选择性的方式制备难以获得的五取代环丙烷. 在低至 0.1 mol% 的低催化剂负载下，展示了Rh I /二烯配合物的非凡高性能。