methyl (Z)-4-phenylbut-3-enoate | 91083-82-8

• 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: methyl (Z)-4-phenylbut-3-enoate
• CAS: 91083-82-8
• 化学式: C₁₁H₁₂O₂
• 分子量: 176.215
• InChiKey: VOEDRUGFNJEWGQ-YVMONPNESA-N

物化性质

• 沸点：
  277.6±19.0 °C(Predicted)
• 密度：
  1.055±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 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：

  methyl (Z)-4-phenylbut-3-enoate 在 二异丁基氢化铝 作用下， 以 二氯甲烷 、 二乙二醇二甲醚 、 甲苯 为溶剂， 反应 4.0h， 生成 2,3 cis-2-(2,2-difluoro-3-phenylcyclopropyl)acetaldehyde 、 (2E,4Z)-4-fluoro-5-phenylpenta-2,4-dienal
  参考文献：
  名称：

  宝石-二氟环丙烷的立体选择性开环：立体定义的（E，E）-和（E，Z）-共轭氟二烯的入口

  摘要：

  描述了宝石-二氟环丙基乙醛的开环，它们选择性地产生（E，E）-和（E，Z）共轭的二氟二烯。提出了两种立体发散方法，可从一个常见的前体中获得两种立体异构体，并具有高收率和选择性。讨论了这些转换的机械方面。

  DOI：

  10.1002/chem.201704956
• 作为产物：
  描述：

  3-苯-1-丙炔 在 甲醇 、 六甲基磷酰三胺 、 甲基锂 、 potassium carbonate 、 lithium diisopropyl amide 作用下， 以 丙酮 为溶剂， 反应 10.92h， 生成 methyl (Z)-4-phenylbut-3-enoate
  参考文献：
  名称：

  (Z)-.alpha.-(trimethylsilyl) .alpha.,.beta.-unsaturated esters. Their stereoselective conversion into .alpha.,.beta.- and .beta.,.gamma.-unsaturated esters and .beta.,.gamma.-unsaturated ketene acetals

  摘要：

  Deprotonation of methyl (Z)-alpha-(trimethylsilyl) alpha,beta-unsaturated esters with lithium diisopropylamide (LDA) or with lithium hexamethyldisilazide (LHMDS) in the presence of hexamethylphosphoramide (HMPA) as an activator, followed by protonation of the intermediate dienolates with methanol, produces stereoselectively the desilylated (E)-3-alkenoic esters. Trapping the dienolates with chlorotrimethylsilane instead of methanol and then treatment of the resultant ketene acetals with aqueous hydrochloric acid affords (E)-alpha-(trimethylsilyl)-beta,gamma-alkenoic esters in 98% isomeric purities. In the absence of HMPA, (Z)-alpha-(trimethylsilyl)-alpha, beta-alkenoic esters undergo a Michael-type addition with LDA to furnish, after methanol-mediated elimination of the diisopropylamine moiety, (E)-alpha-(trimethylsilyl)-alpha,beta-alkenoic esters. In contrast to the behavior with the corresponding Z esters, deprotonation of the E esters with LDA does not require an activator. Treatment of the dienolate intermediates formed with chlorotrimethylsilane yields (O-methyl-C,O-bis(trimethylsilyl)ketene acetals, and alkylation furnishes (E)-alpha-alkyl beta,gamma-unsaturated esters. Protodesilylation of the latter compounds with tetra-n-butylammonium fluoride followed by hydrolytic workup provides trisubstituted 2-alkenoates.

  DOI：

  10.1021/jo00007a039

文献信息

• Photo-induced energy transfer relay of N-heterocyclic carbene catalysis: an asymmetric α-fluorination/isomerization cascade
  作者：Xinhang Jiang、En Li、Jiean Chen、Yong Huang

  DOI：10.1039/d0cc07264h

  日期：——

  transfer process that leads to selective access of chiral allylic fluorides with a cis-olefin geometry. In the absence of a photocatalyst or light, the reaction proceeds smoothly to give (E)-olefin products, while the (Z)-isomer can be obtained under photosensitizing conditions. Preliminary mechanistic experiments suggest that an energy transfer process might be operative.

  烯烃产物的几何构型通常由合成中的热力学控制来驱动。能够切换顺/反选择性的方法很少。最近，光敏方法已经成为完成该任务的有力工具。在此报告中，我们报告了N-杂环卡宾（NHC）结合的中间体通过光致能量转移过程的原位异构化，该过程导致具有顺式-烯烃几何形状的手性烯丙基氟化物的选择性进入。在没有光催化剂或光的情况下，反应平稳进行，得到（E）-烯烃产物，而（Z异构体可以在光敏条件下获得。初步的机械实验表明，能量传递过程可能有效。
• Short and Efficient Synthesis of Cryptophycin Unit A
  作者：Stefan Eissler、Markus Nahrwold、Beate Neumann、Hans-Georg Stammler、Norbert Sewald

  DOI：10.1021/ol063032l

  日期：2007.3.1

  [reaction: see text] Two short synthetic approaches toward cryptophycin unit A comprise a catalytic asymmetric dihydroxylation as the sole source of chirality, while all further stereogenic centers are introduced under substrate control. The key step of the first route is a vinylogous Mukaiyama aldol addition, which introduces the alpha,beta-unsaturated ester moiety with defined configuration at the

  [反应：见正文]两种针对隐藻霉素A的短合成方法包括催化不对称二羟基化作为手性的唯一来源，而所有其他立体异构中心均在底物的控制下引入。第一条路线的关键步骤是乙烯基乙烯基Mukaiyama羟醛加成，它引入在δ碳原子上具有确定构型的α，β-不饱和酯部分。同样地，与烯丙基三丁基锡烷非对映选择性地烯丙基化，可以通过复分解反应将其转化为单元A前体。
• Direct C–C Bond Formation of Allylic Alcohols with CO₂ toward Carboxylic Acids by Photoredox/Nickel Dual Catalysis
  作者：Zhengning Fan、Shenhao Chen、Song Zou、Chanjuan Xi

  DOI：10.1021/acscatal.2c00418

  日期：2022.3.4

  Carboxylation of allylic alcohols with carbon dioxide is accomplished by photoredox/nickel dual catalysis, generating linear acids exclusively with good Z/E stereoselectivity. Hantzsch ester is employed as the reductant instead of stoichiometric metallic reductants, and the reaction can be conducted under room temperature with a blue LED light source. Mechanistic studies reveal that the presence of

  烯丙醇与二氧化碳的羧基化是通过光氧化还原/镍双重催化完成的，仅生成具有良好Z/E立体选择性的线性酸。采用 Hantzsch 酯代替化学计量的金属还原剂作为还原剂，反应可以在室温下用蓝色 LED 光源进行。机理研究表明，该催化体系中水的存在对反应的成功至关重要，并且反应更有可能在原位形成的烯丙基碳酸氢盐的氧化加成中进行。
• Catalytic Photoredox Carbobromination of Unactivated Alkenes with α-Bromocarbonyls via the Mechanistically Distinct Radical-Addition Radical-Pairing Pathway
  作者：Harshvardhan Singh、Raj K. Tak、Dhruba P. Poudel、Ramesh Giri

  DOI：10.1021/acscatal.4c00955

  日期：2024.4.19

  blue-light-emitting diode (LED) light. The reaction proceeds with α-bromoesters, α-bromonitriles, and α-bromo-γ-lactones along with terminal and 1,2-disubstituted internal alkenes. Reactions with indenes and 1,1-disubstituted alkenes generate alkylated alkenes. Mechanistic studies by product selectivity and three-way competitive crossover experiments suggest that the reaction operates by a radical-addition radical-pairing

  我们公开了在蓝光发光二极管（LED）光下未活化的烯烃与α-溴羰基化合物的催化光氧化还原碳溴化反应。该反应以 α-溴酯、α-溴腈和 α-溴-γ-内酯以及末端和 1,2-二取代的内部烯烃进行。与茚和 1,1-二取代烯烃反应生成烷基化烯烃。通过产物选择性和三向竞争交叉实验进行的机理研究表明，该反应通过自由基加成自由基配对（RARP）机制进行。催化转化是通过 Br –（或 Br 3 –）而不是烷基（R • ）对 PC •+进行单电子还原来实现的，产物是通过 Br •（或 Br 2 •– ) 和R • ，而不是Br –和碳正离子(R + )的组合。
• Nickel-Catalyzed Electrochemical Couplings of Vinyl Halides:  Synthetic and Stereochemical Aspects
  作者：C. Cannes、S. Condon、M. Durandetti、J. Périchon、J.-Y. Nédélec

  DOI：10.1021/jo000182f

  日期：2000.7.1

  Homo- and cross-coupling involving alkenyl halides have been performed efficiently using an electroassisted nickel-complex catalysis. Valuable product such as conjugated dienes, beta,gamma- or gamma,delta-unsaturated esters, ketones, or nitriles, as well as alkenylated aryl compounds are thus prepared with high yields and high stereoselectivity. Partial isomerization is only observed in a few cases, when the alkenyl halide is involved in a late step of the catalytic cycle. This is the case in the preparation of (Z,Z)-1,3-diene.