(E)-N-benzyl-5-iodopent-4-en-1-amine | 1380099-89-7

• 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)-N-benzyl-5-iodopent-4-en-1-amine
• CAS: 1380099-89-7
• 化学式: C₁₂H₁₆IN
• 分子量: 301.17
• InChiKey: FAXFCXULTYVISR-WEVVVXLNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (E)-N-benzyl-5-iodopent-4-en-1-amine 在 四(三苯基膦)钯 、 silver orthophosphate 作用下， 以 2-甲基四氢呋喃 、 水 为溶剂， 以75%的产率得到(E)-1-((R)-1-benzylpyrrolidin-2-yl)-2-((S)-1-benzylpyrrolidin-2-yl)ethene
  参考文献：
  名称：

  Pd-Catalyzed Bis-cyclization/Dimerization Reactions of ω-Aminovinyl Halides

  摘要：

  Palladium is shown to catalyze the dimerization and cyclization of vinyl halides to generate pyrrolidine and piperidine dimers connected by a trans-ethylene bridge. The reaction tolerates a variety of N-alkyl substituents, including adamantyl. This remarkable dimerization reaction generates the skeleton of the alkaloid hyalbidone in a single step. A crossover experiment with a vinyl halide and a vinyl bromide is consistent with a Michael-type addition to a vinylpalladium cation to generate a Pd(0) alkylidene intermediate.

  DOI：

  10.1021/ol401563z
• 作为产物：
  描述：

  pent-4-yn-1-yl methanesulfonate 在 二氯二茂锆 、 二异丁基氢化铝 、 sodium iodide 作用下， 以 四氢呋喃 、 二甲基亚砜 为溶剂， 反应 14.0h， 生成 (E)-N-benzyl-5-iodopent-4-en-1-amine
  参考文献：
  名称：

  Carbenylative Amination with N-Tosylhydrazones

  摘要：

  A Pd-catalyzed reaction of vinyl iodides and N-tosylhydrazones that assembles eta(3)-allyl ligands through carbene insertion is demonstrated. Intramolecular trapping with nitrogen nucleophiles generates good yields of cinnamyl and pentadienyl amines like those found in alkaloid natural products. Carbenylative amination was the key reaction to complete the synthesis of the alkaloid caulophyllumine B. Migratory insertion was biased to provide allylamines with optical purity up to 64% ee, but in a lower yield.

  DOI：

  10.1021/ol301385g

文献信息

• Carbenylative Amination and Alkylation of Vinyl Iodides via Palladium Alkylidene Intermediates
  作者：Ilandari Dewage Udara Anulal Premachandra、Thi A. Nguyen、Chengtian Shen、Eugene S. Gutman、David L. Van Vranken

  DOI：10.1021/acs.orglett.5b02820

  日期：2015.11.6

  palladium-catalyzed reactions involving insertion of alkylidenes with α-hydrogens undergo β-hydride elimination from alkylpalladium(II) intermediates to form alkenes. Vinyl iodides were shown to generate η3-allylpalladium intermediates that resist β-hydride elimination, preserving the sp3 center adjacent to the carbene moiety. Acyclic stereocontrol (syn/anti) for carbenylative amination and alkylation reactions was

  大多数涉及亚烷基与α氢插入的钯催化反应都会从烷基钯（II）中间体中进行β-氢化物消除，从而形成烯烃。碘代乙烯显示出生成η 3个抵抗β-氢消除π-烯丙基中间体，保留SP 3邻近碳烯部分中心。用于羰基化胺化和烷基化反应的无环立体控制（syn / anti）很低，这表明在迁移插入步骤中缺乏控制。受阻严重的卡宾前体莫名其妙地导致形成具有高水平立体控制的Z-烯烃。
• Palladium-Catalyzed Catellani Aminocyclopropanation Reactions with Vinyl Halides
  作者：Avinash Khanna、Ilandari Dewage Udara Anulal Premachandra、Paul D. Sung、David L. Van Vranken

  DOI：10.1021/ol401383m

  日期：2013.6.21

  intramolecular aminocyclopropanation of norbornenes with aliphatic vinyl halides in good yields. The reaction tolerates a variety of amine substituents and gives good results with a variety of carbocyclic and oxabicyclic [2.2.1] alkene acceptors. Notably, stabilized enolate nucleophiles were also employed in cyclopropanation reactions.

  已显示钯以良好的产率催化降冰片烯与脂肪族乙烯基卤化物的分子内氨基环丙烷化。该反应可耐受多种胺取代基，并与多种碳环和氧杂双环[2.2.1]烯烃受体均能获得良好的结果。值得注意的是，稳定化的烯醇盐亲核试剂也用于环丙烷化反应中。
• Palladium/GF-Phos-catalyzed asymmetric carbenylative amination to access chiral pyrrolidines and piperidines
  作者：Yue Sun、Chun Ma、Zhiming Li、Junliang Zhang

  DOI：10.1039/d2sc03999k

  日期：——

  but the development of catalytic enantioselective versions still poses considerable challenges and only very limited examples have been reported. We herein report an asymmetric palladium/GF-Phos-catalyzed carbenylative amination reaction of N-tosylhydrazones and (E)-vinyl iodides pendent with amine, which allows facile access to a range of chiral pyrrolidines and piperidines in good yields (45–93%)

  N-甲苯磺酰腙的交叉偶联已成为构建结构多样化分子的有效方法，但催化对映选择性版本的开发仍然面临相当大的挑战，并且仅报道了非常有限的例子。我们在此报告了一种不对称钯/GF-Phos催化的N-甲苯磺酰腙和( E )-乙烯基碘化物与胺悬垂的羧基胺化反应，该反应可以轻松获得一系列手性吡咯烷和哌啶，产率良好（45-93%） ) 高达 96.5: 3.5 er 。此外，条件温和、底物范围广泛、制备规模化以及天然产物(−)-norruspoline的高效合成是该方法的实用特点。