methyl 2-phenylbut-3-enoate | 25522-59-2

• 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: methyl 2-phenylbut-3-enoate
• CAS: 25522-59-2
• 化学式: C₁₁H₁₂O₂
• 分子量: 176.215
• InChiKey: VFTZDFQTYJJPRO-UHFFFAOYSA-N

物化性质

• 沸点：
  240.5±9.0 °C(Predicted)
• 密度：
  1.029±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 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 2-phenylbut-3-enoate 在 锌 作用下， 以 溶剂黄146 、 甲苯 为溶剂， 反应 14.0h， 生成 1-aza-4β-hydroxy-3α-phenyl-5aαH-bicyclo<4.3.0>nonan-2-one
  参考文献：
  名称：

  Iida, Hideo; Watanabe, Yohya; Kibayashi, Chihiro, Chemical and pharmaceutical bulletin, 1985, vol. 33, # 1, p. 351 - 357

  摘要：

  DOI：
• 作为产物：
  描述：

  苯乙酸甲酯 在 正丁基锂 、 三溴化镓 、 二异丙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 1,2-二氯乙烷 为溶剂， 反应 4.0h， 生成 methyl 2-phenylbut-3-enoate
  参考文献：
  名称：

  烯基醚的三溴化镓催化偶联反应与烯酮甲硅烷基缩醛

  摘要：

  A“Ga'llant夫妇：酯的α烯基化物通过贾布尔完成3链烯基醚和甲硅烷基烯酮缩醛之间催化的耦合。在该反应体系中，各种链烯基醚，包括那些具有乙烯基和取代的链烯基，被适用，并适用烯酮甲硅烷基乙缩醛的范围为足够宽。的机理进行了讨论。

  DOI：

  10.1002/anie.201203778

文献信息

• Rhodium-Catalyzed Allylic Substitution Reactions with Indium(III) Organometallics
  作者：Ricardo Riveiros、Rubén Tato、José Pérez Sestelo、Luis A. Sarandeses

  DOI：10.1002/ejoc.201200104

  日期：2012.5

  novel rhodium-catalyzed allylic substitution reaction using indium organometallics is reported. Aryl- and heteroarylindium reagents reacted in THF at 80 °C with primary and secondary allyl halides and their derivatives under rhodium(I) catalysis to afford the α-substituted products in good yields and with high regio- and stereoselectivity. The reaction takes place with substoichiometric amounts of

  报道了一种使用铟有机金属化合物的新型铑催化烯丙基取代反应。芳基和杂芳基铟试剂在 80°C 的 THF 中与伯和仲烯丙基卤化物及其衍生物在铑 (I) 催化下反应，以良好的收率和高区域和立体选择性提供 α-取代产物。该反应发生在亚化学计量的三有机铟试剂下，这证明了铟-铑金属转移过程在碳-碳键形成反应中的效率。
• Coupling Reaction of Enol Derivatives with Silyl Ketene Acetals Catalyzed by Gallium Trihalides
  作者：Yoshihiro Nishimoto、Yuji Kita、Hiroki Ueda、Hiroto Imaoka、Kouji Chiba、Makoto Yasuda、Akio Baba

  DOI：10.1002/chem.201602150

  日期：2016.8.8

  cross‐coupling reaction between enol derivatives and silyl ketene acetals catalyzed by GaBr3 took place to give the corresponding α‐alkenyl esters. GaBr3 showed the most effective catalytic ability, whereas other metal salts such as BF3⋅OEt2, AlCl3, PdCl2, and lanthanide triflates were not effective. Various types of enol ethers and vinyl carboxylates as enol derivatives are amenable to this coupling

  GaBr 3催化烯醇衍生物与甲硅烷基烯酮缩醛之间发生交叉偶联反应，得到相应的α-烯基酯。GaBr 3表现出最有效的催化能力，而其他金属盐（例如BF 3 OEt 2，AlCl 3，PdCl 2和镧系三氟甲磺酸盐）无效。各种类型的烯醇醚和羧酸乙烯酯作为烯醇衍生物都适合这种偶联。与甲硅烷基乙烯酮缩醛的反应范围也很宽。我们通过NMR光谱法成功地观察到烷基镓中间体，提示了GaBr 3之间涉及抗碳藻糖基化的机理，烯醇衍生物和甲硅烷基烯酮乙缩醛，然后从烷基镓中进行顺-β-烷氧基消除。根据动力学研究，使用乙烯基醚和羧酸乙烯酯的反应限制周转步骤分别涉及顺-β-烷氧基消除和抗羰基镓化反应。因此，离去基团对反应的进行有重要影响。理论计算分析表明，适度的镓路易斯酸将有助于烷基镓中间体的柔性构象变化，并有助于在β-烷氧基消除过程中裂解碳氧键，这是反应中的周转限制步骤。在乙烯基醚和甲硅烷基乙烯酮缩醛之间。
• Synthesis of 2-aryloxy butenoates by copper-catalysed allylic C–H carboxylation of allyl aryl ethers with carbon dioxide
  作者：Atsushi Ueno、Masanori Takimoto、Zhaomin Hou

  DOI：10.1039/c7ob00341b

  日期：——

  2-aryloxy-3-butenoic acid esters by allylic C–H bond carboxylation of allyl aryl ethers with CO2 has been achieved through deprotonative alumination with an aluminium ate compound (iBu3Al(TMP)Li) followed by NHC-copper-catalysed carboxylation of the resulting aryloxy allylaluminum species. Functional groups such as halogens (F, Cl, Br, I), CF3, amino, methylthio, silyloxy and hetero aromatic groups survived the

  通过用铝酸酯化合物（i Bu 3 Al（TMP）Li）然后进行NHC的去质子化铝，通过烯丙基芳基醚与CO 2的烯丙基C–H键羧化烯丙基C–H键羧化，可以有效合成2-芳氧基-3-丁烯酸酯-铜催化的芳氧基烯丙基铝物种的羧化反应。诸如卤素（F，Cl，Br，I），CF 3，氨基，甲硫基，甲硅烷氧基和杂芳族基团的官能团在反应条件下幸存下来。2-芳氧基-3-丁烯酸酯产物的区域和立体选择性转化（异构化）为（Z在催化量的DBU存在下也已经获得了）-2-芳氧基-2-丁烯酸酯异构体。因此，这些转化构成了一种有效的方案，用于使用CO 2作为C1结构单元，从单一的烯丙基芳基醚底物发散合成2－芳氧基3－2和2－丁烯酸酯。
• Catalytic, <i>contra</i>-Thermodynamic Positional Alkene Isomerization
  作者：Gino Occhialini、Vignesh Palani、Alison E. Wendlandt

  DOI：10.1021/jacs.1c12043

  日期：2022.1.12

  The positional isomerization of C═C double bonds is a powerful strategy for the interconversion of alkene regioisomers. However, existing methods provide access to thermodynamically more stable isomers from less stable starting materials. Here, we report the discovery of a dual catalyst system that promotes contra-thermodynamic positional alkene isomerization under photochemical irradiation, providing

  C=C双键的位置异构化是烯烃区域异构体相互转化的有力策略。然而，现有方法提供了从不太稳定的起始材料获得热力学上更稳定的异构体的途径。在这里，我们报告了在光化学辐照下促进逆热力学位置烯烃异构化的双催化剂系统的发现，提供了直接从共轭的内部烯烃起始材料获得末端烯烃异构体的途径。该方法的实用性在多种富电子/贫电子烯烃的去共轭中以及通过对天然产物合成的战略应用得到证明。机理研究与区域特异性双分子均裂取代（S H2') 机制通过烯丙基钴肟中间体进行。
• Cyclopropanation of benzylidenemalononitrile with dialko×ycarbenes and free radical rearrangement of the cyclopropanes
  作者：Nadine Merkley、Paul C. Venneri、John Warkentin

  DOI：10.1139/cjc-79-3-312

  日期：——

  Thermolysis of 2-cinnamyloxy-2-methoxy-5,5-dimethyl-Delta (3)-1,3,4-oxadiazoline (1a) and the analogous 2-benzyloxy-2-methoxy compound (1b) at 110 degreesC, in benzene containing benzylidenemalononitrile, afforded products of apparent regiospecific addition of methoxycarbonyl and cinnamyl (or benzyl) radicals to the double bond. When the thermolysis of 1a was run with added TEMPO, methoxycarbonyl and cinnamyl radicals were captured. Thermolysis of the 2,2-dibenzyloxy analogue (1c) in the presence of benzylidenemalononitrile gave an adduct that is formally the product of addition of benzyloxycarbonyl and benzyl radicals to the double bond. In this case, a radical addition mechanism could be ruled out, because the rate constant for decarboxylation of benzyloxycarbonyl radicals is very large. A mechanism that fits all of the results is predominant cyclopropanation of benzylidenemalononitrile by the dialkoxycarbenes derived from the oxadiazolines, in competition with fragmentation of the carbenes to radical pairs. The cyclopropanes so formed then undergo homolytic ring-opening to the appropriate diradicals. Subsequent beta -scission of the diradicals to afford radical pairs, and coupling of those pairs, gives the final products. Thus, both carbene and radical chemistry are involved in the overall processes.