ethyl (E)-4-((4-methylphenyl)sulfonamido)but-2-enoate

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: ethyl (E)-4-((4-methylphenyl)sulfonamido)but-2-enoate
• 英文别名: ethyl (E)-4-[(4-methylphenyl)sulfonylamino]but-2-enoate
• 化学式: C₁₃H₁₇NO₄S
• 分子量: 283.348
• InChiKey: WYJHSSJWEDDDJH-SNAWJCMRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  80.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl (E)-4-((4-methylphenyl)sulfonamido)but-2-enoate 在 N-[3,5-二(三氟甲基)苯基]-N-[(9R)-6-甲氧基-9-二奎宁基]硫脲 、 palladium 10% on activated carbon 、 甲酸铵 作用下， 以 四氢呋喃 、 乙醇 、 甲苯 为溶剂， 反应 22.0h， 生成 ethyl 2-((3S,4R,5S)-4-amino-5-cyclohexyl-1-tosylpyrrolidin-3-yl)acetate
  参考文献：
  名称：

  Organocatalytic asymmetric synthesis of trisubstituted pyrrolidines via a cascade reaction

  摘要：

  A new bifunctional thiourea II catalyzed methodology was developed for the synthesis of chiral trisubstituted pyrrolidines using 4-aminocrotonate 1a/1b and nitroolefins 2a-g as starting materials. Two different N-protected 4-aminocrotonates la and 1b were tested for the reaction with la giving the desired product 3a with a high diastereomeric ratio (>20:1) but with low enantioselectivity (ee up to 7%). N-Tosyl-4-aminocrotonate 1b, however, yielded the product with moderate dr (up to 68:32) but with high ee in the case of the major trans-trans-isomers 4a-g (ee from 92% to 98%) and modest enantiomeric excess for the minor trans-cis-isomers 4a'-g' (ee up to 57%). This methodology was also successfully applied when (E)-beta-methyl-trans-beta-nitrostyrene 2h was used as the starting nitroalkene to provide the product with dr 70/30 and with ee of 63% and 67%, respectively. The absolute configuration of both isomers was established using chiral derivatization with Mosher's and mandelic acids, with the relative stereochemistry being determined via NMR analysis. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.01.021
• 作为产物：
  描述：

  4-溴巴豆酸乙酯 在 potassium carbonate 、 三氟乙酸 、 potassium iodide 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 3.0h， 生成 ethyl (E)-4-((4-methylphenyl)sulfonamido)but-2-enoate
  参考文献：
  名称：

  Discovery of Inhibitors of the Lipopolysaccharide Transporter MsbA: From a Screening Hit to Potent Wild-Type Gram-Negative Activity

  摘要：

  DOI：

  10.1021/acs.jmedchem.1c01909

文献信息

• Highly enantio- and diastereoselective organocatalytic cascade aza-Michael–Michael reactions: a direct method for the synthesis of trisubstituted chiral pyrrolidines
  作者：Hao Li、Liansuo Zu、Hexin Xie、Jian Wang、Wei Wang

  DOI：10.1039/b812464g

  日期：——

  An unprecedented highly enantio- and diastereoselective cascade aza-Michael-Michael reaction of alpha,beta-unsaturated aldehydes with trans-gamma-Ts protected amino alpha,beta-unsaturated ester has been developed; the simple and practical process, efficiently catalyzed by chiral diphenylprolinol TMS ether, serves as a powerful access to highly functionalized trisubstituted chiral pyrrolidines.

  已经开发出前所未有的高度对映体和非对映体选择性的α，β-不饱和醛与反式-γ-Ts保护的氨基α，β-不饱和酯的氮杂-Michael-Michael级联反应；简单而实用的方法，通过手性二苯基脯氨醇TMS醚有效催化，可以有效地获得高度官能化的三取代手性吡咯烷。
• (−)-(3S)-3-(Tosylamino)butano-4-lactone, a Versatile Chiral Synthon for the Enantioselective Synthesis of Different Types of Polyamine Macrocycles: Determination of the Absolute Configuration of (−)-(R)-Budmunchiamine A
  作者：Richard Detterbeck、Armin Guggisberg、Kasim Popaj、Manfred Hesse

  DOI：10.1002/1522-2675(200206)85:6<1742::aid-hlca1742>3.0.co;2-e

  日期：2002.6

  (−)-(3S)-3-(Tosylamino)butano-4-lactone (1) and its derivative ethyl (−)-(3S)-4-iodo-3-(tosylamino)butanoate (2) are presented as easily accessible chiral building blocks for the construction of a range of different macrolactam frameworks important for the synthesis of naturally occurring polyamine alkaloids as well as for establishing a substance library of such compounds, including S-containing derivatives

  (-)-(3S)-3-(Tosylamino)butano-4-lactone (1) 及其衍生物 (-)-(3S)-4-iodo-3-(tosylamino)butanoate (2) 很容易呈现用于构建一系列不同的大环内酰胺骨架，这些骨架对于合成天然存在的多胺生物碱以及建立此类化合物的物质库很重要，包括用于生物测试的含硫衍生物。除此之外，根据新方法通过全合成确定了来自合欢的精胺生物碱 (-)-(R)-budmunchiamine A (3) 的绝对构型。
• P^III-Mediated intramolecular cyclopropanation and metal-free synthesis of cyclopropane-fused heterocycles
  作者：Jiayong Zhang、Jiahang Hao、Zhiqiang Huang、Jie Han、Zhengjie He

  DOI：10.1039/d0cc04086j

  日期：——

  A P(NMe2)3-mediated reductive intramolecular cyclopropanation is developed for the first time, which provides facile access to a wide variety of cyclopropane-fused heterocycles including chromanes, tetrahydroquinolines, lactones, and lactams. Catalytic hydrogenative ring-expansion of the cyclopropane-fused heterocycles is also elaborated, leading to various structurally important medium-sized heterocycles

  首次开发了AP（NMe 2）3介导的还原性分子内环丙烷化反应，该反应可轻松利用各种环丙烷稠合的杂环，包括苯并二氢吡喃，四氢喹啉，内酯和内酰胺。还详细说明了环丙烷稠合杂环的催化加氢扩环，从而产生了各种结构上重要的中等尺寸的杂环。
• Enantioselective Cascade Michael-Michael Reactions and Related Catalysts
  申请人：Wang Wei

  公开号：US20110172438A1

  公开（公告）日：2011-07-14

  The invention provides direct processes and related catalysts for the syntheses of trisubstituted chiral pyrrolidines, piperidines, tetrahydrothiophenes, and thianes by highly enantio- and diastereoselective cascade Michael-Michael reaction of α, β-unsaturated aldehydes with trans-γ-protected amino α, β-unsaturated esters.

  本发明提供了直接合成三取代手性吡咯烷、哌啶、四氢噻吩和硫杂环己烷的过程及相关催化剂，通过高对映选择性和对映异构体选择性的级联迈克尔-迈克尔反应，将α，β-不饱和醛与转-γ-保护氨基α，β-不饱和酯反应。
• Enantioselective Synthesis of Pyrrolidines by a Phosphine-Catalyzed γ-Umpolung/β-Umpolung Cascade
  作者：Jeremy T. Maddigan-Wyatt、Jing Cao、Jhi Ametovski、Joel F. Hooper、David W. Lupton

  DOI：10.1021/acs.orglett.2c00785

  日期：2022.4.22

  Herein, we report an enantioselective catalytic annulation of electron-poor allenes with aminocrotonates. The reaction proceeds by the umpolung γ-amination of the allenoate and β-umpolung intramolecular conjugate addition. The reaction provides ready access to pyrrolidines using a homochiral phosphepine catalyst, which allows most products to form in good yields (55–85%) with ≥95:5 er and ≥4:1 dr.

  在这里，我们报道了一种对电子贫丙二烯与氨基巴豆酸酯的对映选择性催化环化。该反应通过烯丙酸酯的 umpolung γ-胺化和 β-umpolung 分子内共轭加成来进行。该反应使用纯手性膦催化剂提供了容易获得吡咯烷的途径，这使得大多数产物以≥95:5 er 和≥4:1 dr 的良好产率 (55–85%) 形成。辅助串联催化变体也是可行的，并且报告了支持所提出的反应途径的机理研究。