(E)-Methyl 4-(4-cyanophenyl)-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-(4-cyanophenyl)-2-oxobut-3-enoate
• 英文别名: methyl (E)-4-(4-cyanophenyl)-2-oxobut-3-enoate
• 化学式: C₁₂H₉NO₃
• 分子量: 215.208
• InChiKey: TWSUJOKSRUZEGR-VOTSOKGWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  67.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (E)-Methyl 4-(4-cyanophenyl)-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)-4-cyanostyryl)-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

文献信息

• Enantioselective Mukaiyama–Michael Reaction of β,γ-Unsaturated α-Keto Esters with Silyl Ketene Acetals Catalyzed by a Chiral Magnesium Phosphate
  作者：Hualing He、Xizhe Shen、Xinying Ding、Jon C. Antilla

  DOI：10.1021/acs.orglett.2c04277

  日期：2023.2.10

  We would like to describe an efficient and highly enantioselective Mukaiyama–Michael reaction of silyl ketene acetals with β,γ-unsaturated α-keto esters catalyzed by a chiral magnesium BINOL-derived phosphate. The resulting functionalized 1,5-dicarbonyl adducts are obtained in high yields (up to 96%) and with excellent enantioselectivities (up to 98%) under mild conditions. Two plausible mechanistic

  我们想描述一种高效且高度对映选择性的 Mukaiyama-Michael 反应，甲硅烷基乙烯酮缩醛与 β,γ-不饱和 α-酮酯，由手性镁 BINOL 衍生的磷酸盐催化。由此产生的功能化 1,5-二羰基加合物在温和条件下以高收率（高达 96%）和出色的对映选择性（高达 98%）获得。提出了两个似是而非的机制途径，包括 1,4-加成和杂 Diels-Alder [4 + 2] 环加成。
• Chiral<i>N</i>,<i>N′</i>-Dioxide-Yttrium Triflate Complexes-Catalyzed Asymmetric Aldol Cyclization of α-Keto Esters with α-Isothiocyanato Imide
  作者：Xiaohu Zhao、Mingsheng Xie、Xiaohua Liu、Yulong Zhang、Xiao Xiao、Lili Lin、Xiaoming Feng

  DOI：10.1002/adsc.201300593

  日期：2013.11.11

  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