1-苄基-2-甲基-1,2,3,4-四氢异喹啉 | 10225-29-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异喹啉及其衍生物
• 中文名称: 1-苄基-2-甲基-1,2,3,4-四氢异喹啉
• 英文名称: 1-benzyl-2-methyl-1,2,3,4-tetrahydroisoquinoline
• 英文别名: (-+)-1-benzyl-2-methyl-1,2,3,4-tetrahydro-isoquinoline；(-+)-1-Benzyl-2-methyl-1,2,3,4-tetrahydro-isochinolin；1-Benzyl-2-methyl-1,2,3,4-tetrahydro-isochinolin；1-benzyl-2-methyl-3,4-dihydro-1H-isoquinoline
• CAS: 10225-29-3
• 化学式: C₁₇H₁₉N
• 分子量: 237.345
• InChiKey: VKRKVLLLTIHDEF-UHFFFAOYSA-N

物化性质

• 沸点：
  215-218 °C(Press: 14 Torr)
• 密度：
  1.051±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-苄基-2-甲基-1,2,3,4-四氢异喹啉 在 manganese(IV) oxide 、 硫酸 作用下， 生成 2-methyl-3,4-dihydroisoquinolinium iodide
  参考文献：
  名称：

  Pyman, Journal of the Chemical Society, 1909, vol. 95, p. 1747

  摘要：

  DOI：
• 作为产物：
  描述：

  2-methyl-3,4-dihydroisoquinolinium iodide 在 萘 、 lithium 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 2.83h， 生成 1-苄基-2-甲基-1,2,3,4-四氢异喹啉
  参考文献：
  名称：

  Alkali Metal-mediated Synthesis of 1- and 4-Substituted N-Alkyl-1,2,3,4-tetrahydro- isoquinolines

  摘要：

  Reductive cleavage by electron transfer from Li or K metal of 1-alkoxy-substituted N-alkyltetrahydroisoquinolines led to the formation of organometallic derivatives. Quenching of these intermediates with electrophilic reagents afforded 1- or 4-substituted N-alkyl-1,2,3,4-tetrahydroisoquinolines, depending upon the nature of the metal.

  DOI：

  10.3987/com-03-9936

文献信息

• Reactions of Alkyl, Benzyl and Stannyl Halides with Lewis Acid Complexed <i>α</i>-Lithiated Tertiary Amines
  作者：Satinder V. Kessar、Paramjit Singh、Kamal N. Singh、Sandeep K. Singh

  DOI：10.1055/s-2001-12324

  日期：——

  α-Amino stannanes can be obtained readily from tertiary amines through BF3 promoted deprotonation; in situ CsF treatment of BF3 complexed stannanes followed by lithium-transmetalation can be used to procure those α-alkylation products which are not available directly.

  α-氨基锡烷可以通过三甲胺经BF3促进的脱质子化反应而方便地获得；通过BF3复合锡烷在位CsF处理后进行锂的金属转移反应，可以得到那些不能直接获得的α-烷基化产物。
• Phosphazene base-catalyzed hydroamination of aminoalkenes for the construction of isoindoline scaffolds: Application to the total synthesis of aristocularine
  作者：Junpei Matsuoka、Maki Terashita、Akari Miyawaki、Kiyoshi Tomioka、Yasutomo Yamamoto

  DOI：10.1016/j.tetlet.2021.153599

  日期：2022.1

  A method for isoindoline synthesis via phosphazene base-catalyzed intramolecular hydroamination of aminoalkenes was developed. The reaction has a broad functional group tolerance, including for halide, cyano, and methoxy groups, and could also be used to synthesize tetrahydroisoquinoline, pyrrolidine, and piperidine. The method was used as a key step in the total synthesis of aristocularine in six

  建立了磷腈碱催化氨基烯烃分子内加氢胺化合成异二氢吲哚的方法。该反应具有广泛的官能团耐受性，包括卤化物、氰基和甲氧基，也可用于合成四氢异喹啉、吡咯烷和哌啶。该方法被用作马兜铃碱全合成的关键步骤，分六步进行，总产率为 35%。该策略涉及通过控制所需 C N 键的形成来构建异二氢吲哚核心，而相对不稳定的甲氧基甲基和芳基溴保持完整。
• Synthesis of 1-Substituted Tetrahydroisoquinolines by Lithiation and Electrophilic Quenching Guided by In Situ IR and NMR Spectroscopy and Application to the Synthesis of Salsolidine, Carnegine and Laudanosine
  作者：Xiabing Li、Daniele Leonori、Nadeem S. Sheikh、Iain Coldham

  DOI：10.1002/chem.201301096

  日期：2013.6.10

  The lithiation of N‐tert‐butoxycarbonyl (N‐Boc)‐1,2,3,4‐tetrahydroisoquinoline was optimized by in situ IR (ReactIR) spectroscopy. Optimum conditions were found by using n‐butyllithium in THF at −50 °C for less than 5 min. The intermediate organolithium was quenched with electrophiles to give 1‐substituted 1,2,3,4‐tetrahydroisoquinolines. Monitoring the lithiation by IR or NMR spectroscopy showed that

  的锂化ñ -叔丁氧羰基（Ñ -Boc）-1,2,3,4-四氢异喹啉用原位IR（的ReactIR）光谱进行了优化。通过在-50°C下于THF中使用正丁基锂少于5分钟发现了最佳条件。用亲电子试剂淬灭中间体有机锂，得到1-取代的1,2,3,4-四氢异喹啉。通过IR或NMR光谱监测锂化表明，一个旋转异构体反应迅速，并且通过可变温度NMR光谱确定了Boc基团的旋转势垒，发现其约为60.8 kJ mol -1，相当于在−50°C下旋转约30 s的半衰期。（-）-天冬氨酸作为配体的使用在亲电淬灭后导致低水平的对映选择性，“穷人霍夫曼试验”表明有机锂在构型上不稳定。该化学方法应用于N -Boc-6,7-二甲氧基-1,2,3,4-四氢异喹啉，并导致外消旋生物碱salsolidine，carnegine，norlaudanosine和laudanosine的有效合成。
• Simultaneous engineering of an enzyme's entrance tunnel and active site: the case of monoamine oxidase MAO-N
  作者：Guangyue Li、Peiyuan Yao、Rui Gong、Jinlong Li、Pi Liu、Richard Lonsdale、Qiaqing Wu、Jianping Lin、Dunming Zhu、Manfred T. Reetz

  DOI：10.1039/c6sc05381e

  日期：——

  A new directed evolution approach is presented to enhance the activity of an enzyme and to manipulate stereoselectivity by focusing iterative saturation mutagenesis (ISM) simultaneously on residues lining the entrance tunnel and the binding pocket. This combined mutagenesis strategy was applied successfully to the monoamine oxidase from Aspergillus niger (MAO-N) in the reaction of sterically demanding

  提出了一种新的定向进化方法，通过同时将迭代饱和诱变（ISM）集中在入口通道和结合袋内的残基上来增强酶的活性并操纵立体选择性。这种组合诱变策略已成功应用于黑曲霉单胺氧化酶（MAO-N）在空间要求底物的反应中，该底物对基于苯并哌啶支架的手性药物的合成感兴趣。在( S )-1,2,3,4-四氢-1-甲基-异喹啉、( S )-1,2,3,4-四氢-1-的合成中实现了Turner型去消旋化对映选择性的逆转乙基异喹啉和( S )-1,2,3,4-四氢-1-异丙基异喹啉。广泛的分子动力学模拟表明，催化特性的改变是由于入口隧道的疏水性增加与结合袋形状的改变相一致。
• A New Method of α-Functionalization for Tertiary Amines by Nucleophilic Substitution of α-Siloxy Amines
  作者：Norihiro Tokitoh、Renji Okazaki

  DOI：10.1246/bcsj.61.735

  日期：1988.3

  α-Siloxy amines, which were easily prepared by “silicon Polonovski reaction” of tertiary amine N-oxides with trialkylsilyl trifluoromethanesulfonate, were treated with various nucleophiles to give the corresponding α-functionalized tertiary amines in moderate to good yields. This new method has the advantage that it enables the α-substitution of amines not only by alkyl groups but also by alkenyl and

  α-甲硅烷氧基胺很容易通过叔胺 N-氧化物与三氟甲磺酸三烷基甲硅烷基酯的“硅波洛诺夫斯基反应”制备，用各种亲核试剂处理，以中等至良好的产率得到相应的 α-官能化叔胺。这种新方法的优点是，它不仅可以通过烷基，而且可以通过以 sp2 碳为反应中心的烯基和芳基对胺进行 α 取代，因为在偶极稳定的亲电取代中引入这些基团是困难的。 α-锂硫胺。除了有机金属化合物如格氏试剂和有机铝试剂外，三甲基氰化甲硅烷和甲硅烷基烯醇醚也可以在适当的路易斯酸存在下用作亲核试剂。