ethyl (Z)-2-iodo-4-oxobutenoate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl (Z)-2-iodo-4-oxobutenoate
• 英文别名: ethyl (Z)-2-iodo-4-oxobut-2-enoate
• 化学式: C₆H₇IO₃
• 分子量: 254.024
• InChiKey: PYJSSFHPZUFQBM-HYXAFXHYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  ethyl (Z)-2-iodo-4-oxobutenoate 在 N-甲基吗啉 、 bis-triphenylphosphine-palladium(II) chloride 、 sodium chlorite 、 copper(l) iodide 、 sodium dihydrogenphosphate dihydrate 、 2-甲基-2-丁烯 、 sodium hydride 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 邻二甲苯 、 水 、 mineral oil 、 叔丁醇 为溶剂， 反应 9.59h， 生成 4-ethoxycarbonyl-6-(2-naphthyl)-1-(p-toluenesulfonyl)-1,6-dihydropyridin-2(3H)-one
  参考文献：
  名称：

  New type of azacyclization: thermal preparation of 4,6-disubstituted 2-piperidinone from N-sulfonyldienamide and its substituent effect

  摘要：

  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.

  DOI：

  10.1016/j.tetlet.2011.12.014

文献信息

• Synthesis of 2,4,6-Trisubstituted Chiral Piperidines and (−)-Dendroprimine by One-Pot Asymmetric Azaelectrocyclization Protocol
  作者：Toyoharu Kobayashi、Futoshi Hasegawa、Katsunori Tanaka、Shigeo Katsumura

  DOI：10.1021/ol0614065

  日期：2006.8.1

  [reaction: see text] Stereocontrolled synthesis of 2,4,6-trisubstituted piperidine diastereomers has been realized from common intermediates, obtained by a one-pot azaelectrocyclization protocol. Based on the method, the asymmetric synthesis of an indolizidine alkaloid, (-)-dendroprimine, was achieved.

  [反应：见正文]由一锅氮杂电环化方案获得的常见中间体已经实现了2,4,6-三取代哌啶非对映异构体的立体控制合成。基于该方法，实现了吲哚并立定生物碱（-）-dendroprimine的不对称合成。
• 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。
• Library-directed Solution- and Solid-phase Synthesis of 2,4-Disubstituted Pyridines: One-pot Approach through 6 π-Azaelectrocyclization
  作者：Taku Sakaguchi、Toyoharu Kobayashi、Sho Hatano、Hiroshi Tsuchikawa、Koichi Fukase、Katsunori Tanaka、Shigeo Katsumura

  DOI：10.1002/asia.200900146

  日期：2009.10.5

  for the synthesis of 2,4‐disubstituted pyridines has been successfully established. The method proceeds through a 6π‐azaelectrocyclization‐aromatization sequence. Using this method, a wide variety of pyridine structures substituted at the 2‐position have been rapidly constructed from vinyl stannanes, vinyl iodide, sulfonamide, and a palladium catalyst. The method was further applied to the solid‐phase

  已经成功地建立了一种有效的一锅合成方法，用于合成2,4-二取代的吡啶。该方法通过6π-氮杂电环化-芳香化序列进行。使用这种方法，已经迅速从乙烯基锡烷，乙烯基碘，磺酰胺和钯催化剂构建了在2位取代的吡啶结构。该方法进一步应用于固相合成，其中使用“无痕”磺酰胺连接剂可以快速制备少量的高纯度吡啶类化合物，而无需进行色谱分离。
• Total Synthesis of (−)-Hippodamine by Stereocontrolled Construction of Azaphenalene Skeleton Based on Extended One-Pot Asymmetric Azaelectrocyclization
  作者：Shintaro Fujita、Taku Sakaguchi、Toyoharu Kobayashi、Hiroshi Tsuchikawa、Shigeo Katsumura

  DOI：10.1021/ol4010917

  日期：2013.6.7

  The first asymmetric total synthesis of (-)-hippodamine has been accomplished via the concise construction of its azaphenalene core, which Is featured by the 2,4,6-chiral piperidine synthesis based on one-pot asymmetric azaelectrocyclization in the partially activated substituent system and the subsequent intramolecular Mannich reaction.
• Development of a One-Pot Asymmetric Azaelectrocyclization Protocol:  Synthesis of Chiral 2,4-Disubstituted 1,2,5,6-Tetrahydropyridines
  作者：Toyoharu Kobayashi、Miyuki Nakashima、Toshikazu Hakogi、Katsunori Tanaka、Shigeo Katsumura

  DOI：10.1021/ol061405c

  日期：2006.8.1

  A one-pot procedure for tetracyclic chiral aminoacetals, the useful precursors for substituted piperidine synthesis, has been established via Stille-Migita coupling, 6 pi-azaelectrocyclization, and aminoacetal formation from readily prepared vinylstannanes, vinyliodides, and cis-aminoindanol derivatives. Based on the method, chiral 2,4-disubstituted 1,2,5,6-tetrahydropyridines, bearing a variety of aromatic substituents at the C-2 position, have been prepared.