1-[N-(4-methoxybenzyl)amino]-5-hexyne

• 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: 1-[N-(4-methoxybenzyl)amino]-5-hexyne
• 英文别名: N-(4-methoxybenzyl)-5-hexyn-1-amine；N-(4-methoxybenzyl)hex-5-yn-1-amine；N-[(4-methoxyphenyl)methyl]hex-5-yn-1-amine
• 化学式: C₁₄H₁₉NO
• 分子量: 217.311
• InChiKey: KJTFHCWOEVBACB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  21.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-[N-(4-methoxybenzyl)amino]-5-hexyne 在 二氯二茂锆 、 苄基三乙基氯化铵 、 二异丁基氢化铝 、 lithium tert-butoxide 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 (E)-1-(4-methoxybenzyl)-2-styrylpiperidine
  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：

  N-(5-己炔基)酞酰亚胺 在 盐酸 、 sodium tetrahydroborate 、 三乙胺 作用下， 以 甲醇 、 乙醚 、 水 、 异丙醇 为溶剂， 反应 3.17h， 生成 1-[N-(4-methoxybenzyl)amino]-5-hexyne
  参考文献：
  名称：

  Synthesis of Strained 1,3-Diene Macrocycles via Copper-Mediated Castro–Stephens Coupling/Alkyne Reduction Tandem Reactions

  摘要：

  A copper-mediated macrocyclization involving the reaction of a vinyl iodide and a terminal alkyne followed by an in situ reduction of the enyne intermediate is reported. The reaction generates a conjugated Z-double bond within a strained medium-size lactone, lactam, or ether macrocycle. A variety of macrocyclic compounds bearing different ring sizes and functionalities were synthesized. A complementary stepwise procedure was also developed for less strained ring systems.

  DOI：

  10.1021/acs.orglett.5b01892

文献信息

• Catalytic One-Pot Synthesis of Cyclic Amidines by Virtue of Tandem Reactions Involving Intramolecular Hydroamination under Mild Conditions
  作者：Sukbok Chang、Minjae Lee、Doo Young Jung、Eun Jeong Yoo、Seung Hwan Cho、Sun Kyu Han

  DOI：10.1021/ja064788i

  日期：2006.9.1

  A new synthetic methodology for the generation of cyclic amidines has been developed by the reaction of 1,n-aminoalkynes with electron-deficient azides using a ruthenium catalyst at ambient temperature. The reaction proceeds most likely via a tandem sequence of intramolecular hydroamination of aminoalkynes, cycloaddition of azides with the resulting enamines, and rearrangement of triazoline intermediates

  通过在环境温度下使用钌催化剂使 1,n-氨基炔烃与缺电子叠氮化物反应，开发了一种用于生成环脒的新合成方法。该反应最有可能通过氨基炔烃的分子内加氢胺化、叠氮化物与所得烯胺的环加成以及三唑啉中间体的重排的串联顺序进行。作为原理证明，它证明了平衡级联序列可以由不可逆步骤有利地驱动，从而使简便的一锅合成路线能够在前所未有的温和条件下提供分子复杂性，而无需依赖传统的线性方法。
• Carbenylative Amination with <i>N</i>-Tosylhydrazones
  作者：Avinash Khanna、Charles Maung、Kyle R. Johnson、Tom T. Luong、David L. Van Vranken

  DOI：10.1021/ol301385g

  日期：2012.6.15

  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.
• Synthesis of Strained 1,3-Diene Macrocycles via Copper-Mediated Castro–Stephens Coupling/Alkyne Reduction Tandem Reactions
  作者：Wei Li、Christopher M. Schneider、Gunda I. Georg

  DOI：10.1021/acs.orglett.5b01892

  日期：2015.8.7

  A copper-mediated macrocyclization involving the reaction of a vinyl iodide and a terminal alkyne followed by an in situ reduction of the enyne intermediate is reported. The reaction generates a conjugated Z-double bond within a strained medium-size lactone, lactam, or ether macrocycle. A variety of macrocyclic compounds bearing different ring sizes and functionalities were synthesized. A complementary stepwise procedure was also developed for less strained ring systems.