methyl 2-diazo-2-phenylacetate | 178547-58-5

• 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: methyl 2-diazo-2-phenylacetate
• 英文别名: methyl phenyldiazoacetate；methyl 2-imino-2-phenylacetate；Methyl 2-imino-2-phenylacetate
• CAS: 178547-58-5
• 化学式: C₉H₉NO₂
• 分子量: 163.176
• InChiKey: KASWPDSOXKQVOZ-UHFFFAOYSA-N

物化性质

• 沸点：
  225.4±23.0 °C(Predicted)
• 密度：
  1.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  50.2
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 2-diazo-2-phenylacetate 在 盐酸 、 三乙胺 作用下， 以 四氢呋喃 、 乙醚 、 乙酸乙酯 为溶剂， 反应 2.58h， 生成 苯甲酰甲酸甲酯
  参考文献：
  名称：

  Koeppen, Juergen; Matthies, Dieter; Schweim, Harald, Liebigs Annalen der Chemie, 1985, # 12, p. 2383 - 2389

  摘要：

  DOI：
• 作为产物：
  描述：

  methyl 2-azido-2-phenylacetate 在 ([2,5-Me2-3,4-Ph2(η5-C4CNHPh)]Ru(CO)(μ-CO))2 作用下， 以 四氢呋喃 为溶剂， 生成 methyl 2-diazo-2-phenylacetate
  参考文献：
  名称：

  C–H Activation Guided by Aromatic N–H Ketimines: Synthesis of Functionalized Isoquinolines Using Benzyl Azides and Alkynes

  摘要：

  Aromatic N-H ketimines were in situ generated from various benzylic azides by ruthenium catalysis for the subsequent Rh-catalyzed annulation reaction with alkynes to give the corresponding isoquinolines. In contrast to conventional synthetic methods for aromatic NH ketimines, our protocol works under mild and neutral conditions, which enabled the synthesis of isoquinolines having various functionalities such as carbonyl, ester, alkenyl, and ether groups. In addition, the imidates generated from alpha-azido ethers were successfully used for the synthesis of 1-alkoxyisoquinolines.

  DOI：

  10.1021/jo501465q

文献信息

• [EN] 1,3-SUBSTITUED PYRAZOLE COMPOUNDS USEFUL FOR REDUCTION OF VERY LONG CHAIN FATTY ACIC LEVELS<br/>[FR] COMPOSÉS PYRAZOLE 1,3-SUBSTITUÉS UTILES POUR LA RÉDUCTION DE NIVEAUX D'ACIDES GRAS À CHAÎNE TRÈS LONGUE
  申请人：VERTEX PHARMA

  公开号：WO2018107056A1

  公开（公告）日：2018-06-14

  Disclosed are chemical entities which are compounds of Formula (I) and pharmaceutically acceptable salts thereof, wherein Formula (I) has the structure: R1a, R1b, R2, R3, R4a, R4b and Y are as defined herein. These chemical entities are useful for reduction of very long chain fatty acid levels. These chemical entities and pharmaceutically acceptable compositions comprising such chemical entities can be useful for treating various diseases, disorders and conditions, such as adrenoleukodystrophy (ALD).

  揭示了化学实体，它们是具有式（I）的化合物及其药学上可接受的盐，其中式（I）具有结构：R1a，R1b，R2，R3，R4a，R4b和Y如本文所定义。这些化学实体对于降低非常长链脂肪酸水平是有用的。这些化学实体和包括这些化学实体的药学上可接受的组合物可用于治疗各种疾病、疾病和症状，如肾上腺白质脑白质营养不良（ALD）。
• Enantioselective Palladium(II) Phosphate Catalyzed Three-Component Reactions of Pyrrole, Diazoesters, and Imines
  作者：Dan Zhang、Huang Qiu、Liqin Jiang、Fengping Lv、Chaoqun Ma、Wenhao Hu

  DOI：10.1002/anie.201306824

  日期：2013.12.9

  Reaction trio: The title reaction delivers CH functionalized pyrrole derivatives in moderate to good yields. This novel three‐component reaction provides both syn‐ and anti‐pyrrole derivatives having two contiguous stereocenters with good regio‐, diastereo‐, and enantioselectivity. This process represents the first highly enantioselective palladium‐carbenoid‐mediated reaction.

  反应三重反应：标题反应以中等至良好的产率提供CH官能化的吡咯衍生物。这种新颖的三组分反应可同时提供具有两个连续立体中心的顺式和反吡咯衍生物，并具有良好的区域，非对映和对映选择性。该过程代表了第一个高度对映选择性的钯-类胡萝卜素介导的反应。
• Visible Light Induced Metal-Free Carbene <i>N</i>-Carbazolation
  作者：Claire Empel、Frederic W. Patureau、Rene M. Koenigs

  DOI：10.1021/acs.joc.9b01753

  日期：2019.9.6

  Metal-free N–H functionalization reactions represent an important strategy for sustainable C–N coupling reactions. In this report, we describe the visible light photolysis of aryl diazoacetates in the presence of some N-heterocycles that enables mild, metal-free N–H functionalization reactions of carbazole and azepine heterocycles (15 examples, up to 83% yield).

  无金属的N–H官能化反应代表了可持续的C–N偶联反应的重要策略。在本报告中，我们描述了在存在一些N-杂环的情况下可见光对芳族重氮乙酸酯的光解作用，该分解过程可实现咔唑和氮杂杂环的温和，无金属的NH功能化反应（15个实例，产率高达83％）。
• New Tandem Reactions of Metal Carbenoids. Intermolecular Formation of Azomethine Ylide from Methyl 2-Diazo-2-phenylacetate and Schiff Base: Intramolecular 1,3-Dipolar Cycloaddition
  作者：A. F. Khlebnikov、M. S. Novikov、A. A. Bespokoev、R. R. Kostikov、J. Kopf、Z. A. Starikova、M. Yu. Antipin

  DOI：10.1007/s11178-005-0267-y

  日期：2005.6

  Rhodium acetate-catalyzed decomposition of methyl 2-diazo-2-phenylacetate in the presence of substituted N-methylbenzylideneamines possessing an activated alkenyl fragment (dipolarophile) in the side chain gives products of intramolecular cycloaddition of intermediate Z,E- and E,Z-azomethine ylides. The cycloaddition is regioselective, and the products are hexahydrochromeno[4,3-b]pyrrole derivatives. The stereoselectivity of the process depends on the temperature. In the temperature range from 20 to 80°C, the major stereoisomer is that with cis junction of the tetrahydropyran and pyrrolidine rings. N-Phenylazomethine ylides generated from methyl 2-diazo-2-phenylacetate and alkyl 4-[2-(phenyliminomethyl)phenoxy]-2-butenoates at 40°C undergo cyclization to aziridines at a higher rate, as compared to the rate of cycloaddition to the internal dipolarophile. N-Phenylazomethine ylides generated by thermolysis of the corresponding aziridine or by the “deprotonation” method react with equal regio- and stereoselectivity to give intramolecular cycloaddition products, hexahydrochromeno[4,3-b]pyrrole derivatives with trans-fused tetrahydropyran and pyrrolidine rings. Analysis of the experimental and calculation data suggests preference of the endo transition state in the cycloaddition of the examined azomethine ylides.

  在侧链中具有活化烯基片段（亲偶极试剂）的取代的 N-甲基亚苄基胺存在下，醋酸铑催化 2-重氮-2-苯基乙酸甲酯分解，得到中间体 Z,E- 和 E,Z- 的分子内环加成产物偶氮甲碱叶立德。环加成反应具有区域选择性，产物为六氢苯并[4,3-b]吡咯衍生物。该过程的立体选择性取决于温度。在20～80℃的温度范围内，主要的立体异构体是四氢吡喃环和吡咯烷环顺式连接的立体异构体。与环加成速率相比，由 2-重氮-2-苯基乙酸甲酯和 4-[2-(苯基亚氨基甲基)苯氧基]-2-丁烯酸烷基酯在 40°C 生成的 N-苯基甲亚碱叶立德以更高的速率环化为氮丙啶到内部亲偶极子。通过热解相应的氮丙啶或通过“去质子化”方法产生的N-苯基甲亚碱叶立德以相同的区域选择性和立体选择性反应，得到分子内环加成产物，即具有反式稠合四氢吡喃和吡咯烷环的六氢苯并[4,3-b]吡咯衍生物。对实验和计算数据的分析表明，在所检测的偶氮甲碱叶立德的环加成中优选内过渡态。
• PROTEIN CRYSTAL OF HUMAN CYTOCHROME P450 AROMATASE AND USES THEREOF
  申请人：GHOSH Debashis

  公开号：US20090204378A1

  公开（公告）日：2009-08-13

  The present invention relates to a protein crystal of at least one binding site of a human aromatase. The present invention also relates to a fully processed human cytochrome P450 aromatase and a protein crystal thereof. The present invention further relates to methods of making and using the aromatase and the protein crystal thereof.

  本发明涉及人类芳香化酶至少一个结合位点的蛋白晶体。本发明还涉及完全加工的人类细胞色素P450芳香化酶及其蛋白晶体。本发明还涉及制备和使用芳香化酶及其蛋白晶体的方法。