methyl α-phenyl-α-((phenyl(methoxycarbonyl)methylene)hydrazono)acetate | 72410-77-6

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: methyl α-phenyl-α-((phenyl(methoxycarbonyl)methylene)hydrazono)acetate
• 英文别名: dimethyl 2,2′-(hydrazine-1,2-diylidene)bis(2-phenylacetate)；dimethyl 2,2’-(hydrazine-1,2-diylidene) (2,2’)-bis(2-phenylacetate)；methyl 2-[(2-methoxy-2-oxo-1-phenylethylidene)hydrazinylidene]-2-phenylacetate
• CAS: 72410-77-6
• 化学式: C₁₈H₁₆N₂O₄
• 分子量: 324.336
• InChiKey: BLVTZYGYZSNPCH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.23
• 重原子数：
  24.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  77.32
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为产物：
  描述：

  a-叠氮基-苯乙酸甲酯 在 [Cp*RhI₂]₂ 、 1,4-环己二烯 作用下， 以 氘代氯仿 为溶剂， 反应 12.0h， 生成 methyl α-phenyl-α-((phenyl(methoxycarbonyl)methylene)hydrazono)acetate
  参考文献：
  名称：

  环戊二烯基铑 (III) 配合物作为重氮乙酸苯酯插入 E-H 键的催化剂

  摘要：

  铑 (III) 配合物催化重氮化合物生成的类胡萝卜素插入 E-H 键（E = B、Si、N，但不是 C），尽管效率低于经典的羧酸铑 (II)，尽管形式上更高的氧化态金属。

  DOI：

  10.1016/j.mencom.2022.07.017

文献信息

• Blue LED-Mediated N–H Insertion of Indoles into Aryldiazoesters at Room Temperature in Batch and Flow: Reaction Kinetics, Density Functional Theory, and Mechanistic Study
  作者：Debajit Maiti、Ranajit Das、Subhabrata Sen

  DOI：10.1021/acs.joc.0c02649

  日期：2021.2.5

  blue light-mediated N–H insertion of indole and its derivatives into aryldiazoesters has been reported in a batch and flow strategy to afford the corresponding N-alkylated product in moderate-to-excellent yield. Detailed high-performance liquid chromatography-based reaction kinetics measurements, control experiments, and kinetic isotope effect reveal that 3-substituted indoles with electron-withdrawing

  间歇和流动策略已报道了轻度蓝光介导的吲哚及其衍生物在芳基重氮化合物中的NH插入，从而以中等至优异的产率提供了相应的N-烷基化产物。详细的基于高效液相色谱的反应动力学测量，对照实验和动力学同位素效应表明，带有吸电子基团（例如-CN和-CHO）的3取代的吲哚有助于产物的形成，而给电子基团则阻碍了处理。他们之间表现出中立的吲哚。此外，基于Hammett图和基于密度泛函理论的过渡态优化研究表明，吲哚C3位置取代基的电子性质与N–H插入反应的速率之间存在显着相关性。
• Photolytic amino etherification reactions of aryl diazoacetates with N-heterocycles and a stoichiometric amount of dioxane/tetrahydropyran in aqueous medium: synthesis of 1,4-dioxepane/1,4,7-dioxazonan-6-one systems
  作者：Debajit Maiti、Ranajit Das、Subhabrata Sen

  DOI：10.1039/d1gc02797b

  日期：——

  reaction, various aryl diazoacetates were converted to oxonium ylides by reacting with 1,4-dioxane and THP. These ylides generated in aqueous medium (under metal- and base-free conditions) were then used for the amino etherification of the aforementioned heterocycles in excellent yield. The ylides underwent a [1,2] shift to afford substituted 1,4-dioxepanes. Phthalimide products were also converted

  在此，我们报道了重氮乙酸芳基酯与化学计量量的 1,4-二恶烷/四氢吡喃 (THP) 和各种杂环如吲哚、吡咯、邻苯二甲酰亚胺、噻唑烷二酮和乙内酰脲在水中的蓝色 LED 介导反应。在反应过程中，各种重氮乙酸芳基酯通过与​​ 1,4-二恶烷和 THP 反应转化为氧鎓叶立德。这些在水性介质中（在无金属和无碱条件下）产生的叶立德然后以优异的收率用于上述杂环的氨基醚化。叶立德经历了 [1,2] 转变以提供取代的 1,4-二氧杂环己烷。邻苯二甲酰亚胺产品也被转化为 1,4,7-dioxazonan-6-ones。反应动力学、哈米特图和 DFT 计算（溶剂相）使叶立德的形成和随后与亲核试剂的反应合理化。该反应也以多克规模进行了证明。这种重氮乙酸芳基酯在水性介质中的氨基醚化反应证明了将有毒的 1,4-二恶烷转化为杂环官能化的可持续过程。
• Catalytic Asymmetric C−H Activation of Alkanes and Tetrahydrofuran
  作者：Huw M. L. Davies、Tore Hansen、Melvyn Rowen Churchill

  DOI：10.1021/ja994136c

  日期：2000.4.1

  Rhodium carbenoids derived from methyl aryldiazoacetates are capable of effective catalytic asymmetric C−H activation of a range of alkanes and tetrahydrofuran by a C−H insertion mechanism. Dirhodium tetrakis(S-(N-dodecylbenzenesulfonyl)prolinate) (Rh2(S-DOSP)4) catalyzed decomposition of methyl aryldiazoacetates in the presence of alkanes results in intermolecular C−H insertions with good control

  衍生自重氮基乙酸甲酯的铑类卡宾能够通过 CH 插入机制有效催化不对称 CH 活化一系列烷烃和四氢呋喃。Dirhodium tetrakis(S-(N-dodecylbenzosulfonyl)prolinate) (Rh2(S-DOSP)4) 在烷烃存在下催化重氮基乙酸甲酯的分解导致分子间 C-H 插入，并能很好地控制区域选择性、非对映选择性和对映选择性。衍生自重氮乙酸甲酯的类卡宾比衍生自重氮乙酸的类卡宾具有更高的化学选择性。他们强烈支持将 C-H 插入二级和三级位点。由于卡宾二聚而形成的副产物不是衍生自芳基重氮乙酸酯的卡宾铑的主要问题。
• Copper-Catalyzed Synthesis of 2,4-Disubstituted Allenoates from α-Diazoesters
  作者：Matthew Hassink、Xiaozhong Liu、Joseph M. Fox

  DOI：10.1021/ol2006242

  日期：2011.5.6

  α-substituted-α-diazoesters with terminal alkynes to give substituted allenoates is described. Key to the development of a selective method was the recognition that an adventitous base catalyzes the isomerization to form the allenoate product. A plausible mechanism is proposed, based in part on evidence against a mechanism that involves a Cu(I)-acetylide as a low-valent intermediate.

  描述了一种用于将 α-取代-α-重氮酯与末端炔烃偶联以产生取代的烯丙酸酯的 Cu 催化方法。开发选择性方法的关键是认识到外来碱催化异构化形成烯丙酸酯产物。提出了一种合理的机制，部分基于反对将 Cu(I)-乙炔化物作为低价中间体的机制的证据。
• Transition metal-mediated reductive coupling of diazoesters
  作者：Amanda Grass、Sebastian A. Stoian、Richard L. Lord、Stanislav Groysman

  DOI：10.1039/c9cc03771c

  日期：——

  The first transition metal mediated reductive coupling of diazoesters through the terminal nitrogens is reported. The resulting tetrazene-bridged bis(diazenylacetate) serves as a novel dinucleating ligand to iron(III). DFT calculations suggest that the reductive coupling takes place via a κ2 intermediate, which induces significant radical character on the terminal nitrogen.

  报道了通过末端氮的第一过渡金属介导的重氮酯的还原偶联。所得四烯桥连的双（二氮杂烯基乙酸酯）用作铁（III）的新型双核配体。DFT计算表明，还原偶合发生经由一个κ 2中间，其诱导在末端氮显著自由基字符。