(E)-methyl 4-(2-chlorophenyl)-2-oxobut-3-enoate

• 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 4-(2-chlorophenyl)-2-oxobut-3-enoate
• 英文别名: methyl (E)-4-(2-chlorophenyl)-2-oxobut-3-enoate
• 化学式: C₁₁H₉ClO₃
• 分子量: 224.644
• InChiKey: CLUXXBGVAMIESI-VOTSOKGWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.09
• 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 4-(2-chlorophenyl)-2-oxobut-3-enoate 在 4-二甲氨基吡啶 作用下， 以 二氯甲烷 为溶剂， 生成 3-tert-butyl 5-methyl 5-((E)-2-chlorostyryl)-4-(2-oxooxazolidine-3-carbonyl)-2-thioxooxazolidine-3,5-dicarboxylate
  参考文献：
  名称：

  手性N，N'-二氧化钇-三氟甲基磺酸盐配合物-α-异硫氰基酰亚胺催化α-酮基酯的不对称醛醇缩合环化反应

  摘要：

  AbstractA highly effective aldol cyclization of α‐isothiocyanato imide to both β,γ‐unsaturated α‐keto esters and aryl‐substituted α‐keto esters has been developed. A chiral N,N′‐dioxide–yttrium triflate complex was used as the catalyst. A series of cyclic thiocarbamates bearing chiral quaternary stereocenters was synthesized in good to high yields, excellent diastereo‐ (up to 25:1 dr) and enantioselectivities (up to 99 % ee). In addition, the reaction could be carried out on a gram‐scale, and other functionalized derivatives are also conveniently transformed. Interestingly, a discrepancy of diastereoselection was observed between the reactions of β,γ‐unsaturated α‐keto esters and aryl‐substituted α‐keto esters. Moreover, a substrate dependency of non‐linear effects was observed in this reaction. On the basis of the experimental results and the absolute configuration of the products, possible catalytic models have been proposed to explain the origin of the asymmetric process.magnified image

  DOI：

  10.1002/adsc.201300593
• 作为产物：
  描述：

  1-氯-2-(二甲氧基甲基)苯 在 三氟化硼乙醚 、 silica gel 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 14.0h， 生成 (E)-methyl 4-(2-chlorophenyl)-2-oxobut-3-enoate
  参考文献：
  名称：

  不对称的Cu（ii）-吲哚基甲醇络合物催化2-乙烯基吲哚与β，γ-不饱和α-酮酸酯的Diels-Alder反应：制备官能化四氢咔唑的有效途径†

  摘要：

  已经开发了一种有效的不对称的2-乙烯基吲哚与β，γ-不饱和α-酮酸酯的Diels-Alder反应，用于官能化四氢咔唑的构建。以高产率（高达96％）和良好的立体选择性（ee高达95％，dr高达＞ 99∶1）获得产物。

  DOI：

  10.1039/c4ob00196f

文献信息

• Stereoselective Synthesis of Highly Functionalized Nitrocyclopropanes through the Organocatalyic Michael‐Addition‐Initiated Cyclization of Bromonitromethane and β,γ‐Unsaturated α‐Ketoesters
  作者：Haijian Yu、Qiaohui Wang、Youming Wang、Haibing Song、Zhenghong Zhou、Chuchi Tang

  DOI：10.1002/asia.201300778

  日期：2013.11

  A highly diastereo‐ and enantioselective cyclopropanation of β,γ‐unsaturated α‐ketoesters with bromonitromethane has been successfully developed through a domino Michael‐addition/intramolecular‐alkylation strategy. Acceptable yields (up to 89 %) and enantioselectivities (up to 96 % ee) have been obtained.

  通过多米诺骨牌迈克尔加成/分子内烷基化策略已成功开发出具有溴硝基甲烷的高度非对映和对映选择性的环丙烷化的β，γ-不饱和α-酮酸酯。获得了可接受的收率（最高89％）和对映选择性（最高96％ee）。
• F^–-Free Deoxyhydrotrifluoromethylation of α-Keto Esters with Ph₃P⁺CF₂CO₂^–: Synthesis of α–CF₃-Substituted Esters
  作者：Ying Zheng、Yimin Jia、Yuan Yuan、Zhong-Xing Jiang、Zhigang Yang

  DOI：10.1021/acs.joc.0c01518

  日期：2020.8.21

  direct deoxyhydrotrifluoromethylation of α-keto esters with a difluoromethylating reagent has been achieved, in which the employment of water can promote the dissociation of the CF2 group to form a CF3 moiety, which provides the successful transformation. The current protocol demonstrates one of the most practical approaches to generate α-trifluoromethyl esters with a broad substrate scope and high functional

  三氟甲基化的化合物通常是通过使用CF 3 SiMe 3和NaSO 2 CF 3，梅本氏试剂和Togni试剂通过三氟甲基化反应获得的。在此，已经实现了用二氟甲基化试剂的α-酮酯的外部无氟阴离子的直接脱氧氢三氟甲基化，其中水的使用可以促进CF 2基团的离解以形成CF 3。部分，提供成功的转化。当前方案证明了一种最实用的方法来生产具有广泛的底物范围和高官能团相容性的α-三氟甲基酯，其中它适用于生物活性化合物的后期修饰，并且可以轻松按比例放大。机理研究表明，原位生成的宝石-二氟烯烃中间体会被水分解，从而生成酰基氟和HF。
• 4,5-DIHYDRO-1H-PYRAZOLE DERIVATIVE OR SALTS THEREOF, AND PHARMACEUTICAL COMPOSITION COMPRISING SAME
  申请人：YUHAN CORPORATION

  公开号：US20150291563A1

  公开（公告）日：2015-10-15

  The present invention provides a 4,5-dihydro-1H-pyrazole derivative or its pharmaceutically acceptable salt, a process for the preparation thereof, and a pharmaceutical composition comprising the same. The 4,5-dihydro-1H-pyrazole derivative or its pharmaceutically acceptable salt effectively increases the LXR transcriptional activity, and therefore can be usefully applied for preventing or treating a dysfunction in cholesterol metabolism, such as cholesterol gallstone, hyperlipidemia, or coronary atherosclerosis.

  本发明提供了一种4,5-二氢-1H-吡唑烷衍生物或其药用可接受盐，以及其制备方法和包含该衍生物的药物组合物。4,5-二氢-1H-吡唑烷衍生物或其药用可接受盐有效增加LXR转录活性，因此可以有效地用于预防或治疗胆固醇代谢功能障碍，如胆固醇结石、高脂血症或冠状动脉粥样硬化。
• 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。
• High enantioselective Michael addition of malonates to β,γ-unsaturated α-ketoesters catalyzed by bifunctional thioureas
  作者：Swapna Konda、John C.-G. Zhao

  DOI：10.1016/j.tetlet.2014.07.112

  日期：2014.9

  A highly enantioselective Michael addition of malonates to β,γ-unsaturated α-ketoesters was achieved using cinchona alkaloid-derived thioureas as the bifunctional catalyst. The corresponding Michael addition products were obtained in excellent yields (90–99%) and ee values (up to >99% ee) using a quinidine-derived thiourea as the catalyst under neat conditions. The opposite enantiomer may be obtained

  使用金鸡纳生物碱衍生的硫脲作为双功能催化剂，可将丙二酸酯高度对映体选择性的迈克尔加成到β，γ-不饱和的α-酮酸酯中。在纯净条件下，使用奎尼丁衍生的硫脲作为催化剂，可以以优异的收率（90–99％）和ee值（高达> 99％ee）获得相应的迈克尔加成产物。可以使用奎宁或辛可尼定衍生的硫脲作为催化剂获得相反的对映异构体。