(E)-1-(N-p-toluenesulfonyl-3-indolyl)-2-tributylstannylethene

• 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: (E)-1-(N-p-toluenesulfonyl-3-indolyl)-2-tributylstannylethene
• 英文别名: (E)-(N-p-toluenesulfonylindol-3-yl)-tributyltin
• 化学式: C₂₉H₄₁NO₂SSn
• 分子量: 586.426
• InChiKey: JKCNKQKCECERHG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.59
• 重原子数：
  34
• 可旋转键数：
  13
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  47.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-1-(N-p-toluenesulfonyl-3-indolyl)-2-tributylstannylethene 在 bis-triphenylphosphine-palladium(II) chloride 、 tris-(dibenzylideneacetone)dipalladium(0) 、 copper(l) iodide 、 1,2-双(二苯基膦)乙烷 作用下， 以 1,4-二氧六环 、 甲苯 为溶剂， 反应 2.0h， 生成 4-ethoxycarbonyl-6-(n-p-toluenesulfonyl-3-indolyl)-1-(p-toluenesulfonyl)-1,6-dihydropyridin-2(3H)-one
  参考文献：
  名称：

  Palladium-Catalyzed Asymmetric 6-Endo Cyclization of Dienamides with Substituent-Driven Activation

  摘要：

  Chiral 2-piperidinone compounds with various C-6 substituents were successfully synthesized via a Pd-catalyzed asymmetric 6-endo cyclization of dienamides, which were evidently activated by both N-p-toluenesulfonyl and C-3 ester substituents.

  DOI：

  10.1021/ol300737t

文献信息

• Stereocontrolled Synthesis of Substituted Chiral Piperidines viaOne-Pot Asymmetric 6π-Azaelectrocyclization: Asymmetric Syntheses of(−)-Dendroprimine, (+)-7-Epidendroprimine, (+)-5-Epidendroprimine, and (+)-5,7-Epidendroprimine
  作者：Toyoharu Kobayashi、Futoshi Hasegawa、Yoshikatsu Hirose、Katsunori Tanaka、Hajime Mori、Shigeo Katsumura

  DOI：10.1021/jo202350z

  日期：2012.2.17

  presence of a Pd(0) catalyst stereoselectively produced the tetracyclic aminoacetal compounds, resulting from the four-bond formation accompanying by controlling the stereochemistry at the two asymmetric centers. The produced cyclic aminoacetals can be regarded as synthetic precursors of substituted chiral piperidines, and the syntheses of 2,4- and 2,4,6-substituted piperidines were realized from the obtained

  烯基乙烯基锡，乙基（Z）-2-碘-4-氧代丁烯酸酯和（-）-7-异丙基-顺式的不对称一锅法6π-氮杂电环化-氨基茚满醇在Pd（0）催化剂存在下立体选择性地产生四环氨基缩醛化合物，这是由于通过控制两个不对称中心的立体化学而伴随的四键形成。可以将产生的环状氨基缩醛视为取代的手性哌啶的合成前体，并且通过与C键合的双键的立体选择性氢化，从获得的氨基缩醛中合成2,4-和2,4,6-取代的哌啶。 -4酯基和氨基缩醛部分的烷基化。此外，吲哚并立生物碱，（-）-dendroprimine及其三种立体异构体（+）-7-乙二苯丙氨酸，（+）-5-乙二苯丙氨酸和（+）-5,7-乙二苯丙氨酸是立体选择性合成的。实现。
• Highly Stereoselective Asymmetric 6π-Azaelectrocyclization Utilizing the Novel 7-Alkyl Substituted <i>cis</i>-1-Amino-2-indanols:  Formal Synthesis of 20-Epiuleine
  作者：Katsunori Tanaka、Shigeo Katsumura

  DOI：10.1021/ja026464+

  日期：2002.8.1

  Highly stereoselective asymmetric 6pi-azaelectrocyclization was achieved with generality, based on the reaction between the (E)-3-carbonyl-2,4,6-trienal compounds and the (-)-7-alkyl-cis-1-amino-2-indanol derivatives as the effective novel chiral amines. Furthermore, the chiral auxiliaries of the cyclized products obtained were efficiently removed by the novel manganese dioxide oxidation under remarkably

  基于 (E)-3-羰基-2,4,6-三烯醛化合物与 (-)-7-烷基-顺-1-氨基-2 之间的反应，普遍实现了高度立体选择性的不对称 6pi-氮杂电环化-茚满醇衍生物作为有效的新型手性胺。此外，在非常温和的条件下，通过新型二氧化锰氧化有效去除了所得环化产物的手性助剂，该方法成功应用于光学活性 20-epiuleine 的正式合成。
• Total synthesis of (−)-20-epiuleinevia stereocontrolled one-pot asymmetric azaelectrocyclization followed by novel 1,4-addition reaction
  作者：Taku Sakaguchi、Shohei Kobayashi、Shigeo Katsumura

  DOI：10.1039/c0ob00627k

  日期：——

  containing the 2,3,4-trisubstituted piperidine core, was achieved using a stereocontrolled one-pot asymmetric 6π-azaelectrocyclization followed by a stereoselective 1,4-addition reaction of the unsaturated ester with a Grignard reagent resulting from the novel neighboring participation of the hydroxyl group in cis-aminoindanol as a chiral nitrogen source.

  包含2,3,4-三取代哌啶核心的吲哚生物碱（-）-20-表青碱的首次不对称全合成是通过立体控制的一锅式不对称6π-氮杂电环化反应，然后进行立体选择性的1,4-不饱和酯与格氏试剂的加成反应，是由于羟基中新的邻位参与 顺式氨基吲哚醇 作为手性氮源
• Efficient synthesis of 2,4,5-trisubstituted 2,5-chiral tetrahydropyridines using a one-pot asymmetric azaelectrocyclization protocol
  作者：Toyoharu Kobayashi、Kenichi Takeuchi、Junichi Miwa、Hiroshi Tsuchikawa、Shigeo Katsumura

  DOI：10.1039/b900897g

  日期：——

  The stereocontrolled synthetic procedure for the preparation of 2,4,5-trisubstituted 2,5-chiral 1,2,5,6-tetrahydropyridines was established using a one-pot asymmetric azaelectrocyclization protocol; the generality of this protocol was demonstrated by synthesizing the title compounds with various aryl and alkenyl substituents at the C-2 position.

  使用一锅式不对称氮杂电环化方案建立了制备2,4,5-三取代的2,5-手性1,2,5,6-四氢吡啶的立体控制合成程序；通过合成在C-2位置带有各种芳基和烯基取代基的标题化合物，证明了该方案的普遍性。
• New type of azacyclization: thermal preparation of 4,6-disubstituted 2-piperidinone from N-sulfonyldienamide and its substituent effect
  作者：Yuya Maekawa、Taku Sakaguchi、Hiroshi Tsuchikawa、Shigeo Katsumura

  DOI：10.1016/j.tetlet.2011.12.014

  日期：2012.2

  The thermal 6-endo cyclization of N-sulfonyl-2,4-dienamide compounds to produce 4,6-disubstituted 2-piperidinone is described. The observed remarkable substituent effect due to the N-sulfonyl and C3 ethoxycarbonyl groups for acceleration of this 6-endo cyclization strongly suggests that the reaction would proceed via the 6 pi-azaelectrocyclization of the intermediary imidic acid. On the contrary, the corresponding 5-formyl and 5-acetyl derivatives rapidly cyclized at room temperature to produce the 5-exo cyclized products. (C) 2011 Elsevier Ltd. All rights reserved.