(E)-methyl 2-oxo-4-(m-tolyl)but-3-enoate | 1148004-81-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: (E)-methyl 2-oxo-4-(m-tolyl)but-3-enoate
• 英文别名: methyl (E)-4-(3-methylphenyl)-2-oxobut-3-enoate
• CAS: 1148004-81-2
• 化学式: C₁₂H₁₂O₃
• 分子量: 204.225
• InChiKey: FPSKZRHJXHYVRZ-VOTSOKGWSA-N

物化性质

• 沸点：
  320.3±35.0 °C(Predicted)
• 密度：
  1.132±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-methyl 2-oxo-4-(m-tolyl)but-3-enoate 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 0.5h， 生成
  参考文献：
  名称：

  钯催化不对称烯丙基胺合成手性α，β-不饱和γ-氨基酯

  摘要：

  已经开发了Pd催化的4-取代的2-乙酰氧基丁-3-烯酸酯与胺的不对称烯丙基胺化，用于手性α，β-不饱和γ-氨基酯的区域特异性合成。可以以高达98％的收率和99％ee的产率获得所需的手性胺化产物，并且可以方便地将其转化为手性γ-氨基酸/醇衍生物和手性γ-内酰胺，然后可以对其进行几种类型的合成手性药物和候选药物。手性γ-氨基酯的优先形成可能归因于烯丙基底物右侧的庞大取代基。这项工作为合成手性α，β-不饱和γ-氨基酯及其衍生物提供了有效的策略。

  DOI：

  10.1021/acs.orglett.7b01904
• 作为产物：
  描述：

  1-(dimethoxymethyl)-3-methylbenzene 在 三氟化硼乙醚 、 silica gel 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 27.0h， 生成 (E)-methyl 2-oxo-4-(m-tolyl)but-3-enoate
  参考文献：
  名称：

  Efficient Enantioselective Synthesis of Dihydropyrans Using a Chiral N,N′-Dioxide as Organocatalyst

  摘要：

  The bifunctional organocatalyst C3 N,N'-dioxide has been successfully applied to the asymmetric cascade Michael/hemiacetalization reaction of alpha-substituted cyano ketones and beta,gamma-unsaturated alpha-ketoesters for the synthesis of multifunctionalized chiral dihydropyrans. The corresponding products were obtained in excellent yields (up to 99%) with high to excellent enantioselectivities (up to 99% ee).

  DOI：

  10.1021/ol400894j

文献信息

• Unexpected Cascade Reactions of <i>Ortho</i> ‐Hydroxyenaminones and β,γ‐Unsaturated α‐Ketoesters to Access Hydrogenated Benzoxazolepolycycles and Pyrrole−Phenol Atropisomers
  作者：Xuguan Bai、Lele Wang、Ziying Zhang、Kuan Zhang、Zhanwei Bu、Yufeng Wu、Wenjing Zhang、Qilin Wang

  DOI：10.1002/adsc.201900950

  日期：2019.11.5

  BF3 ⋅ OEt2‐catalyzed Michael addition/cyclization/dehydration sequence of ortho‐hydroxyenaminones with aromatic or aliphatic aldehyde‐derived β,γ‐unsaturated α‐ketoesters has been achieved to afford a wide range of fused hydrogenated benzoxazole polycycles in 67–95% yields in a highly diastereoselective manner. When isatin‐derived β,γ‐unsaturated α‐ketoesters were employed as substrates, completely different reactivities

  已实现了出乎意料的BF 3  OEt 2催化邻羟基烯酮与芳香族或脂族醛衍生的β，γ-不饱和α-酮酸酯的迈克尔加成/环化/脱水序列，从而在67个范围内提供了多种熔融氢化苯并恶唑多环–95％的非对映选择性很高。当使用由异黄素衍生的β，γ-不饱和α-酮酸酯作为底物时，观察到完全不同的反应性，从而提供了一系列带有氧吲哚取代的N-C轴向手性吡咯-苯酚主链的新型阻转异构体，收率高达97％。此外，进行DFT计算以考虑可能的反应途径和立体化学。
• Lewis acid catalyzed asymmetric [4+2] cycloaddition of cyclobutenones to synthesize α,β-unsaturated δ-lactones
  作者：Qian Yao、Han Yu、Hang Zhang、Shunxi Dong、Fenzhen Chang、Lili Lin、Xiaohua Liu、Xiaoming Feng

  DOI：10.1039/c8cc01040d

  日期：——

  Here we report an efficient asymmetric [4+2] cycloaddition of β,γ-unsaturated α-ketoesters with cyclobutenones. The corresponding products were obtained in good yields (up to 92%) with excellent enantioselectivities (up to 98% ee) and diastereoselectivities (up to >19/1 dr). Moreover, based on the control experiments and previous reports, a possible catalytic cycle was proposed.

  在这里，我们报告了β，γ-不饱和α-酮酸酯与环丁烯酮的有效不对称[4 + 2]环加成反应。获得了具有良好对映选择性（高达98％ee）和非对映选择性（高达> 19/1 dr）的高收率（最高92％）的相应产物。此外，基于控制实验和先前的报道，提出了可能的催化循环。
• Facile synthesis of substituted diaryl sulfones <i>via</i> a [3 + 3] benzannulation strategy
  作者：Xiang-zheng Tang、Lang Tong、Hua-ju Liang、Jie Liang、Yong Zou、Xue-jing Zhang、Ming Yan、Albert S. C. Chan

  DOI：10.1039/c8ob00662h

  日期：——

  base-mediated [3 + 3] benzannulation strategy for the conversion of 1,3-bis(sulfonyl)propenes and β,γ-unsaturated α-ketoesters to diaryl sulfones has been developed. This method provides facile, metal-free and efficient access to highly substituted diaryl sulfones in good to excellent yields. In addition, the sulfonyl group could be easily removed or converted to other functional groups via an organostannane

  已开发出一种由碱介导的[3 + 3]苯环芳构化策略，可将1,3-双（磺酰基）丙烯和β，γ-不饱和α-酮酸酯转化为二芳基砜。该方法可以轻松，无金属且高效地获得高取代的二芳基砜，且收率良好。另外，磺酰基可通过有机锡烷中间体容易地除去或转化为其他官能团。
• A New Strategy for Enantioselective Construction of Multisubstituted Five-Membered Oxygen Heterocycles via a Domino Michael/Hemiketalization Reaction
  作者：Yuan-Zhao Hua、Meng-Meng Liu、Pei-Jin Huang、Xixi Song、Min-Can Wang、Jun-Biao Chang

  DOI：10.1002/chem.201501655

  日期：2015.8.17

  A new highly enantioselective domino Michael/hemiketalization reaction of α‐hydroxyacetophenone with β,γ‐unsaturated α‐keto esters for the synthesis of 2,2,4,5‐tetrasubstituted chiral tetrahydrofurans is reported. With 2 mol % intramolecular dinuclear zinc‐AzePhenol complex prepared in situ from the reaction of multidentate semi‐azacrown ether ligand with ZnEt2, the corresponding anti‐multisubstituted

  报道了α-羟基苯乙酮与β，γ-不饱和α-酮酯的一种新的高对映选择性多米诺骨牌迈克尔/半缩合反应，用于合成2,2,4,5-四取代的手性四氢呋喃。用2摩尔％的分子内的双核锌AzePhenol络合物在从多齿半氮杂冠醚配体与ZnEt反应原位制备2，相应的抗在高达90％的收率得到-multisubstituted四氢呋喃产品，和98％对映体过量（EE）在0°C下放置45分钟。而且，该产物很容易转化为2,3,5-三取代的2,3-二氢呋喃，而没有任何光学活性的损失。
• Asymmetric Binary Acid Catalysis: A Regioselectivity Switch between Enantioselective 1,2- and 1,4-Addition through Different Counteranions of InIII
  作者：Jian Lv、Long Zhang、Yueming Zhou、Zongxiu Nie、Sanzhong Luo、Jin-Pei Cheng

  DOI：10.1002/anie.201101254

  日期：2011.7.11

  You can count on the anion: Simply swapping the anions of an indium Lewis acid leads to a remarkable regioselectivity switch between asymmetric 1,2‐ and 1,4‐addition reactions. N‐protected indoles and β,γ‐unsaturated α‐keto esters gave adducts with excellent enantioselectivity (see scheme).

  您可以指望阴离子：简单地交换铟路易斯酸的阴离子会导致不对称的1,2-和1,4-加成反应之间显着的区域选择性转换。N保护的吲哚和β，γ-不饱和的α-酮酯可形成具有出色对映选择性的加合物（参见方案）。