1-(3,4-Dichlorophenyl)-4-methoxy-3,4-dioxobut-1-en | 42393-13-5

• 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: 1-(3,4-Dichlorophenyl)-4-methoxy-3,4-dioxobut-1-en
• 英文别名: methyl (E)-4-(3,4-dichlorophenyl)-2-oxobut-3-enoate
• CAS: 42393-13-5
• 化学式: C₁₁H₈Cl₂O₃
• 分子量: 259.089
• InChiKey: OGEYNSPZJICQBM-HWKANZROSA-N

物化性质

• 沸点：
  379.9±42.0 °C(Predicted)
• 密度：
  1.378±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.09
• 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：

  1-(3,4-Dichlorophenyl)-4-methoxy-3,4-dioxobut-1-en 在 4-二甲氨基吡啶 、 sodium tetrahydroborate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 3.5h， 生成 methyl (E)-2-acetoxy-4-(3,4-dichlorophenyl)but-3-enoate
  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

文献信息

• 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。
• 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）。
• 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
• Synthesis of Chiral α,β-Unsaturated γ-Amino Esters via Pd-Catalyzed Asymmetric Allylic Amination
  作者：Chao Xia、Jiefeng Shen、Delong Liu、Wanbin Zhang

  DOI：10.1021/acs.orglett.7b01904

  日期：2017.8.18

  A Pd-catalyzed asymmetric allylic amination of 4-substituted 2-acetoxybut-3-enoates with amines has been developed for the regiospecific synthesis of chiral α,β-unsaturated γ-amino esters. The desired chiral aminated products can be obtained in up to 98% yield, and 99% ee and can be conveniently transformed to chiral γ-amino acid/alcohol derivatives and chiral γ-lactams, which can then be subjected

  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。