(S)-ethyl 2-ethoxycarbonyl-3-(3-indolyl)-3-(p-methoxylphenyl)propanoate | 1072095-79-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: (S)-ethyl 2-ethoxycarbonyl-3-(3-indolyl)-3-(p-methoxylphenyl)propanoate
• 英文别名: (S)-ethyl-2-ethoxycarbonyl-3-(3-indolyl)-3-(p-methyoxyphenyl)propanoate；(S)-ethyl 2-ethoxycarbonyl-3-(3-indolyl)-3-(p-methoxyphenyl)propanoate；diethyl 2-[(S)-1H-indol-3-yl-(4-methoxyphenyl)methyl]propanedioate
• CAS: 1072095-79-4
• 化学式: C₂₃H₂₅NO₅
• 分子量: 395.455
• InChiKey: SMUZMLYFRLNLFB-FQEVSTJZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  29
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  77.6
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  吲哚 、 4-甲氧基亚苄基丙二酸二乙酯 在 bis[(S)-4-(isopropyl)oxazoline-2-yl]-2-(thienyl)-ethene 、 copper(II) bis(trifluoromethanesulfonate) 作用下， 以 异丁醇 为溶剂， 反应 12.0h， 以99%的产率得到(S)-ethyl 2-ethoxycarbonyl-3-(3-indolyl)-3-(p-methoxylphenyl)propanoate
  参考文献：
  名称：

  杂亚芳基丙二酸酯衍生的双（恶唑啉）铜（II）配合物催化吲哚与亚炔基丙二酸酯的高对映选择性弗里德-克拉夫特反应

  摘要：

  合成了一系列廉价且易于获得的杂芳基丙二酸酯衍生的双（恶唑啉）配体1和2，并将它们的铜（II）配合物用于吲哚和烷基亚乙基丙二酸酯之间的Friedel-Crafts催化反应，S具有出色的不对称对映选择性-对映异构体（最高> 99％ee）在异丁醇中，R-对映异构体（最高96.5％ee）在二氯甲烷中。

  DOI：

  10.1002/adsc.200900669

文献信息

• Dependence of Enantioselectivity on the Ligand/Metal Ratio in the Asymmetric Michael Addition of Indole to Benzylidene Malonates: Electronic Influence of Substrates
  作者：Alexander Schätz、Ramesh Rasappan、Markus Hager、Anja Gissibl、Oliver Reiser

  DOI：10.1002/chem.200800508

  日期：2008.8.18

  Simple bis(oxazoline) ligands, especially azabis(oxazolines), can promote the copper(II)-catalyzed Michael addition of indoles to benzylidene malonates with up to >99 % ee (ee=enantiomeric excess), provided that the ligand/metal ratio is tuned meticulously with particular regard to the electronic properties of the substrate. Despite a common paradigm followed in many asymmetric catalyses, an excess

  简单的双（恶唑啉）配体，特别是氮杂双（恶唑啉），可以促进铜（II）在吲哚至丙二烯丙二酸酯中的吲哚的迈克尔加成，其ee> 99％（ee =对映体过量），前提是配体/金属比特别地，对衬底的电子特性进行微调。尽管在许多不对称催化中遵循了共同的范例，但是手性配体的过量并不总是有益的。实际上，当使用富含电子的亚苄基丙二酸酯时，必须避免任何过量的配体以达到优异的对映选择性。相反，带有吸电子基团的丙二酸酯需要过量的配体才能获得最佳ee值。光学产率与几个对位取代基的sigma（I）值的相关性显示出S型轨迹。在有添加剂的情况下，
• Synthesis of heteroarylidene malonate derived bis(thiazolines) and their application in the catalyzed Friedel–Crafts reaction
  作者：Lei Liu、Jing Li、Mingan Wang、Fengpei Du、Zhaohai Qin、Bin Fu

  DOI：10.1016/j.tetasy.2011.03.003

  日期：2011.3

  A series of novel heteroarylidene malonate derived bis(thiazoline) ligands 1 and 2 were synthesized and applied to a Friedel-Crafts reaction between indole and alkylidene malonate. The Cu(OTf)(2) complex of ligand 2b bearing a benzyl group afforded moderate to excellent enantioselectivity for the adducts (up to >99% ee). (C) 2011 Elsevier Ltd. All rights reserved.
• Cu(OTf)₂-Catalyzed Asymmetric Friedel–Crafts Alkylation Reaction of Indoles with Arylidene Malonates Using Bis(sulfonamide)-Diamine Ligands
  作者：Jing Wu、Dongping Wang、Fan Wu、Boshun Wan

  DOI：10.1021/jo400747d

  日期：2013.6.7

  highly efficient Cu-catalyzed asymmetric Friedel Crafts alkylation reaction of indoles with arylidene malonates using simple, stable, and easily prepared bis-sulfonamide diamine ligands was developed. The desired products were obtained in up to 99% yield with 96% ee.
• The importance of 1:1 and 1:2 metal–ligand species in chiral copper(II)–bis(oxazoline) complexes for catalytic activity
  作者：Markus Hager、Sebastian Wittmann、Alexander Schätz、Florian Pein、Peter Kreitmeier、Oliver Reiser

  DOI：10.1016/j.tetasy.2010.03.030

  日期：2010.5

  The rate ratio of different copper(II)-bis(oxazoline) complexes for catalytic activity was assessed in a simple competitive experiment. The cumulated product enantioselectivity derived from a mixture of catalysts with antipodal chiral induction provided sufficient information to determine the relative rates in the asymmetric Friedel-Crafts alkylations of indoles with benzylidene malonates. The discovery of non-linear effects in the reaction system investigated gave insights into the active and resting states of the catalysts. This approach can serve as a tool to screen the activities of different catalysts when detailed kinetic measurements are not suggestive. (C) 2010 Elsevier Ltd. All rights reserved.