chlorocarbonyl-diazo-acetic acid ethyl ester | 57072-87-4

• 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: chlorocarbonyl-diazo-acetic acid ethyl ester
• 英文别名: ethyl 2-diazomalonyl chloride；ethyl 3-chloro-2-diazo-3-oxopropanoate；(E)-1-chloro-2-diazonio-3-ethoxy-3-oxoprop-1-en-1-olate
• CAS: 57072-87-4
• 化学式: C₅H₅ClN₂O₃
• 分子量: 176.559
• InChiKey: FSZBIEMCMJRRHG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  45.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  chlorocarbonyl-diazo-acetic acid ethyl ester 在 Rh₂(CF₃CONH)₄ 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 生成 ethyl 1-methyl-2-oxoindoline-3-carboxylate
  参考文献：
  名称：

  Ligand Effects in the Rhodium(II)-Catalyzed Reactions of .alpha.-Diazoamides. Oxindole Formation is Promoted by the Use of Rhodium(II) Perfluorocarboxamide Catalysts

  摘要：

  An improved procedure for the preparation of ethyl 2-diazomalonyl chloride ws developed which involves the reaction of ethyl diazoacetate with triphosgene. Using this diazo acid chloride, it was possible to prepare a variety of diazoamides from substituted amines. The rhodium(II)-catalyzed decomposition of these diazoamides was studied in order to probe the chemoselectivity of the carbenoid intermediates in intramolecular insertion reactions. Rhodium(II) acetate decomposition of N-benzyl-2-diazo-N-phenylmalonamic acid ethyl ester resulted in intramolecular C-H insertion to give ethyl 1,4-diphenyl-2-oxoazetidine-3-carboxylate. By changing the catalyst ligand to trifluoroacetamide, beta-lactam formation was completely suppressed in favor of the aromatic C-H insertion which produces an oxindole as the only detectable product. The competition between aliphatic and aromatic carbon-hydrogen insertion of 2-diazo-N-phenylmalonamic acid ethyl ester provides another example of ligand effectiveness in controlling chemoselectivity in dirhodium(II)-catalyzed metal carbene reactions. Thus, treatment of the N-isobutyldiazoanilide with rhodium(II) acetate results in exclusive aliphatic C-H insertion giving 4,4-dimethyl-2-oxo-1-phenylpyrrolidine-3-carboxylic acid ethyl ester, while the perfluorobutyramide ligand promotes oxidinole formation by aromatic C-H insertion. Several other rhodium(II)-catalyzed reactions were studied and were found to be highly catalyst dependent, rhodium(II) perfluorocarboxamides promoting aromatic C-H insertion, and hence oxindole formation, over O-H insertion, cyclization onto adjacent triple bonds, or cyclization to generate 1,3-dipolar intermediates.

  DOI：

  10.1021/jo00088a028
• 作为产物：
  描述：

  三光气 、 重氮乙酸甲酯 在 吡啶 作用下， 以 苯 为溶剂， 反应 20.0h， 以79%的产率得到chlorocarbonyl-diazo-acetic acid ethyl ester
  参考文献：
  名称：

  Studies towards the Synthesis of AlkylN-(4-Nitrophenyl)-3/2-oxomorpholine-2/3-carboxylates

  摘要：

  AbstractThe syntheses of methyl 4‐(4‐nitrophenyl)‐3‐oxomorpholine‐2‐carboxylate (3a) and ethyl 4‐(4‐nitrophenyl)‐2‐oxomorpholine‐3‐carboxylate (5b), important building blocks for the synthesis of factor Xa inhibitor rivaroxaban analogs with potential dual antithrombotic activity, via Rh2(OAc)4‐catalyzed OH and NH carbene insertion reactions are described.

  DOI：

  10.1002/hlca.201300085

文献信息

• N–O Tethered Carbenoid Cyclopropanation Facilitates the Synthesis of a Functionalized Cyclopropyl-Fused Pyrrolidine
  作者：Dimpy Kalia、Gökce Merey、Min Guo、Herman O. Sintim

  DOI：10.1021/jo400788a

  日期：2013.6.21

  We report a facile approach to a cyclopropyl-fused pyrrolidine, which contains four stereogenic centers, by employing the N–O tethered carbenoid methodology. The synthesis was facilitated by the development of a direct Mitsunobu reaction of alcohols with N-alkyl-N-hydroxyl amides to give diazo precursors, which upon intramolecular cyclopropanation yielded a library of N–O containing cyclopropyl-fused

  我们报告了一种采用N–O系链类胡萝卜素方法的简便方法，该方法可用于环丙基融合的吡咯烷，其中包含四个立体生成中心。醇与N-烷基-N-羟基酰胺的直接Mitsunobu反应的发展促进了合成，从而产生了重氮前体，在分子内进行环丙烷化后，得到了一个由N–O组成的含环丙基稠合双环中间体的文库。对该文库一个成员的N–O部分进行精细加工导致形成所需的吡咯烷环，这表明该方法可用于制备环丙基稠合的杂环。
• New Route to Natural Camptothecin through Isomünchnone Cycloaddition
  作者：Alice Kanazawa、Mauro Muniz、Barbora Baumlová、Natalie Ljungdahl、Andrew Greene

  DOI：10.1055/s-2008-1078205

  日期：——

  A novel approach to camptothecin by [3+2] cycloaddition of an isomünchnone intermediate is described.

  一种新颖的喜树碱合成方法被报道，该方法通过异穆钦内酯中间体的[3+2]环加成反应实现。
• Ligand effects in the rhodium(II) catalysed reactions of diazoamides and diazoimides
  作者：Soyfur Miah、Alexandra M.Z. Slawin、Christopher J. Moody、Scott M. Sheehan、Joseph P. Marino、Mark A. Semones、Albert Padwa、Ian C. Richards

  DOI：10.1016/0040-4020(95)01070-x

  日期：1996.2

  ligands, fluorinated carboxamides strongly promoting attack on aromatic rings in preference to other processes. Decomposition of the diazoimides resulted in intramolecular attack on the carbonyl group to give an ylide which could be trapped inter- or intramolecularly. X-Ray crystal structures are reported for the diazo compounds 2 and 4, the indoles 17 and 25, the β-lactam 20, the cycloheptapyrrolones 24

  由相应的胺或酰胺制备了一系列取代的α-重氮酰胺1-8和重氮酰亚胺9-12。铑（II）催化的重氮酰胺分解导致对芳环的进攻，从而产生羟吲哚或对烷基的进攻，从而产生β-内酰胺或环庚吡咯烷酮。铑类胡萝卜素中间体的化学选择性取决于金属配体，氟化羧酰胺优先于其他过程而强烈促进对芳环的攻击。重氮酰亚胺的分解导致分子内对羰基的攻击，从而产生可被分子间或分子内捕获的叶立德。据报道重氮化合物2和X的X射线晶体结构如图4所示，吲哚17和25，β-内酰胺20，环庚基吡咯烷酮24和28，二聚体29和Pictet Spengler产物39。
• Conformational, steric and electronic effects on the site- and chemoselectivity of the metal-catalyzed reaction of N-bis(trimethylsilyl)methyl, N-(2-indolyl)methyl α-diazoamides
  作者：Bao Zhang、Andrew G. H. Wee

  DOI：10.1039/c2ob25103e

  日期：——

  The Rh(II)- and Cu(II)-catalyzed reactions of N-bis(trimethylsilyl)methyl, N-(2-indolyl)methyl α-diazoamides are investigated to delineate how conformational, steric and electronic factors influence the site- and chemoselectivity of the metallocarbenoid reaction. The N-bis(trimethylsilyl)methyl (N-BTMSM) group is found to be essential in promoting the metallocarbenoid reaction at the N-(2-indolyl)methyl

  研究了N-双（三甲基甲硅烷基）甲基，N-（2-吲哚基）甲基α-重氮酰胺的Rh（II）和Cu（II）催化反应，以描述构象，空间和电子因素如何影响位点和金属类化合物反应的化学选择性。所述Ñ双（三甲基硅烷基）甲基（Ñ -BTMSM）基团被发现是在促进在所述metallocarbenoid反应必需ñ - （2-吲哚基）甲基部分，以及提供有关酰胺N-C微妙但有效的构象的影响α在携带N-C重氮酯σ键α烷氧基甲基侧链，具有出色的位点和化学选择性。通常，发现金属催化的反应有利于在吲哚C（2）-C（3）双键上的金属碳氢化合物加成-C-H，从而得到环丙烷化产物（四环γ-内酰胺）。然而，化学选择性还受空间效应，如在显示Ñ - [2-（3- methylindolyl）]甲基重氮酯，以及由该催化剂所采用的性质在一定程度上，如在该N-C α-烷氧基甲基重氮酰胺。发现四环γ-内酰胺在金属碳烯化合物反应条件下或在酸性条
• Reactivity of differentially substituted bis(diazo) esters in rhodium(II) mediated O-H insertion reactions
  作者：Christopher J. Moody、David J. Miller

  DOI：10.1016/s0040-4020(97)10435-5

  日期：1998.3

  bis(diazo) compounds was prepared in which the two diazo groups are differentially substituted. Rhodium(II) acetate catalysed decomposition in the presence of methanol resulted in exclusive O-H insertion reaction at the more reactive diazo group, the less reactive diazophosphonate remaining intact. With the more active rhodium(II) trifluoroacetamide as catalyst, both diazo groups decomposed simultaneously

  讨论了一个重氮基团在另一重氮基团的存在下的选择性催化分解。制备了一系列的双（重氮）化合物，其中两个重氮基被不同地取代。在甲醇存在下乙酸铑（II）催化的分解导致在反应性较高的重氮基团处发生独家的OH插入反应，反应性较低的重氮膦酸酯保持完整。用更具活性的三氟乙酰胺铑（II）作为催化剂，两个重氮基团同时分解。