(E)-N-benzyl-6-iodohex-5-en-1-amine | 1380099-92-2

• 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-6-iodohex-5-en-1-amine
• CAS: 1380099-92-2
• 化学式: C₁₃H₁₈IN
• 分子量: 315.197
• InChiKey: UGVQBLFKILDMRV-UXBLZVDNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  15.0
• 可旋转键数：
  7.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  12.03
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  benzaldehyde p-toluenesulfonylhydrazone 、 (E)-N-benzyl-6-iodohex-5-en-1-amine 在 苄基三乙基氯化铵 、 lithium tert-butoxide 、 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 三乙胺 、 三苯基膦 作用下， 以 2-甲基四氢呋喃 为溶剂， 以90%的产率得到N-benzyl-2-[(E)-2-phenylethenyl]piperidine
  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
• 作为产物：
  描述：

  5-己炔-1-醇 在 二氯二茂锆 、 二异丁基氢化铝 、 三乙胺 、 sodium iodide 作用下， 以 四氢呋喃 、 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 2.0h， 生成 (E)-N-benzyl-6-iodohex-5-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

• 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。
• Pd-Catalyzed Bis-cyclization/Dimerization Reactions of ω-Aminovinyl Halides
  作者：Avinash Khanna、Ilandari Dewage Udara Anulal Premachandra、Paul D. Sung、David L. Van Vranken

  DOI：10.1021/ol401563z

  日期：2013.7.19

  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.