(E)-methyl 2-((pyridin-2-ylmethylene)amino)acetate | 943319-06-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (E)-methyl 2-((pyridin-2-ylmethylene)amino)acetate
• 英文别名: methyl (E)-2-[(pyridin-2-ylmethylene)amino]acetate；methyl (E)-N-(2-pyridylmethylidene)glycinate
• CAS: 943319-06-0
• 化学式: C₉H₁₀N₂O₂
• 分子量: 178.191
• InChiKey: JQIXBUZFFLWGRP-UXBLZVDNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.67
• 重原子数：
  13.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  51.55
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  4-溴苯基异腈 、 (E)-methyl 2-((pyridin-2-ylmethylene)amino)acetate 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 silver carbonate 作用下， 以 1,4-二氧六环 为溶剂， 反应 24.0h， 以56%的产率得到methyl 1-(4-bromophenyl)-2-(pyridin-2-yl)-1H-imidazole-4-carboxylate
  参考文献：
  名称：

  Azomethine-isocyanide [3+2] cycloaddition to imidazoles promoted by silver and DBU

  摘要：

  一种新的银促进的[3+2]环加成反应已被描述，用于构建一系列重要生物活性分子的1,2,4-三取代咪唑。

  DOI：

  10.1039/c7cc00772h
• 作为产物：
  描述：

  吡啶-2-甲醛 、 甘氨酸甲酯盐酸盐 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 生成 (E)-methyl 2-((pyridin-2-ylmethylene)amino)acetate
  参考文献：
  名称：

  通过与亚氨基酯热1，3-偶极环加成反应实现的多层石墨烯：催化中负载配体的多功能平台†

  摘要：

  通过在NMP或吡啶中对石墨进行轻度声处理获得的多层石墨烯（MLG）通过原子力显微镜（AFM），透射电子显微镜（TEM），拉曼光谱和X射线光电子能谱（XPS）进行了全面表征。然后，通过1,3-偶极环加成反应与偶氮甲亚胺，是由各种亚氨基酯的热1，2-原生质形成的。所得的含有取代的脯氨酸基胺官能团的MLG用XPS表征，并显示出较高的氮负载量，取决于所用的亚氨基酯，其氮负载量为0.6至4.2 at％。在这些功能化的MLG中，探针样品经过酯水解，并用作异质N，O-螯合配体以协调铱原子中心。该负载的配合物还通过XPS进行了表征，并在苯乙酮的氢转移还原中测试了其催化活性，获得了高达85％的收率。此外，该催化剂最多可循环使用四次。

  DOI：

  10.1039/c9cc00939f

文献信息

• Morita–Baylis–Hillman adducts as effective dipolarophiles in Copper(<scp>i</scp>)-catalyzed 1,3-dipolar cycloaddition with azomethine ylides: asymmetric construction of pyrrolidine derivatives containing quaternary stereogenic center
  作者：Huai-Long Teng、He Huang、Hai-Yan Tao、Chun-Jiang Wang

  DOI：10.1039/c1cc11138h

  日期：——

  The first catalytic asymmetric 1,3-dipolar cycloaddition of azomethine ylides with easily accessible Morita-Baylis-Hillman adducts as the dipolarophiles has been developed successfully and provides the highly substituted pyrrolidines bearing a unique quaternary and two tertiary stereogenic centers in excellent diastereoselectivity and up to 97% ee.

  偶氮亲和剂成功开发出了首个催化不对称1,3-偶极环偶氮甲亚胺与Morita-Baylis-Hillman加合物的易加成化合物，并提供了具有独特的四级和两个叔立体中心的高度取代的吡咯烷，具有出色的非对映选择性，最高可达97％ee。
• Switching Diastereoselectivity in Catalytic Enantioselective (3+2) Cycloadditions of Azomethine Ylides Promoted by Metal Salts and Privileged Segphos-Derived Ligands
  作者：Guilherme S. Caleffi、Olatz Larrañaga、Marcos Ferrándiz-Saperas、Paulo R. R. Costa、Carmen Nájera、Abel de Cózar、Fernando P. Cossío、José M. Sansano

  DOI：10.1021/acs.joc.9b00267

  日期：2019.9.6

  Catalytic enantioselective 1,3-dipolar cycloaddition between imino esters and electrophilic alkenes, employing chiral metal complexes derived from copper(I) and silver(I) salts and (S)-DM- or (S)-DTBM-Segphos as ligands produces diastereodivergently exo- or endo-cycloadducts, respectively. The effect of the functional group of the dipolarophile and the fine tuning of the catalyst plays an important

  亚氨基酯与亲电子烯烃之间的催化对映选择性1,3-偶极环加成反应，采用衍生自铜（I）和银（I）盐和（S）-DM-或（S）-DTBM-Segphos的手性金属络合物作为配体，可产生非对映异构体分别是环外加合物或环内加合物。亲双极性体的官能团的作用和催化剂的微调在促进反向非对映选择性中起重要作用。还通过密度泛函理论计算来解释实验观察到的对映选择性和非对映选择性数据的起源，以及观察到的转换的内/外比的起源。
• CuI–Fesulphos complexes: efficient chiral catalysts for asymmetric 1,3-dipolar cycloaddition of azomethine ylides
  作者：Silvia Cabrera、Ramón Gómez Arrayás、Belén Martín-Matute、Fernando P. Cossío、Juan C. Carretero

  DOI：10.1016/j.tet.2007.03.130

  日期：2007.7

  The Cu-I-Fesulphos catalyst system (<= 3 mol %) shows an excellent performance in the asymmetric 1,3-dipolar cycloaddition of azomethine ylides. High to very high levels of reactivity, endo/exo selectivity, and enantioselectivity ( 69->99% ee) are generally achieved with a very wide range of azomethine ylides and dipolarophiles. Based on experimental and computational studies data, a model that accounts for this high enantiocontrol is proposed. (c) 2007 Elsevier Ltd. All rights reserved.
• Stereocontrolled Synthesis of Highly Substituted Proline Esters via [3 + 2] Cycloaddition between N-Metalated Azomethine Ylides and Nitroalkenes. Origins of the Metal Effect on the Stereochemical Outcome
  作者：Mirari Ayerbe、Ana Arrieta、Fernando P. Cossío、Anthony Linden

  DOI：10.1021/jo971212q

  日期：1998.3.1

  The [3 + 2] cycloaddition reaction between several N-metalated azomethine ylides and nitroalkenes has been studied using AgOAc and LiClO4 as metalating reagents in the presence of triethylamine. The reaction is found to be very versatile and can be extended to homochiral nitroalkenes. In general, lithium and silver salts promote preferential formation of the endo and exo cycloadducts, respectively. The presence of a phenol moiety induces a shift toward the exo-cycloadduct even when lithium is used. A model based upon the experimental results obtained and SCF-MO calculations is proposed to explain the variable stereochemical outcome of these reactions.