methyl E-2-(benzyloxyimino)ethanate | 57451-13-5

• 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 E-2-(benzyloxyimino)ethanate
• 英文别名: methyl (2E)-[(benzyloxy)imino]acetate；O-benzyl methyl glyoxylate oxime ether；(E)-[(phenylmethoxy)imino] acetic acid methyl ester；methyl (E)-2-(benzyloxyimino)acetate；methyl (2E)-2-phenylmethoxyiminoacetate
• CAS: 57451-13-5
• 化学式: C₁₀H₁₁NO₃
• 分子量: 193.202
• InChiKey: CVWGSVGJXHIXTE-YRNVUSSQSA-N

物化性质

• 沸点：
  279.9±33.0 °C(Predicted)
• 密度：
  1.07±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  47.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl E-2-(benzyloxyimino)ethanate 在 三乙基硼 、 三氟化硼乙醚 、 三甲基铝 、 三正丁基氢锡 作用下， 以 正己烷 、 二氯甲烷 、 1,2-二氯乙烷 为溶剂， 反应 5.5h， 生成 [3aS-[1(S*),3aα,6α,7aβ]]-hexahydro-8,8-dimethyl-1-[1-oxo-2-[(phenylmethoxy)amino]butyl]-3H-3a,6-methano-2,1-benzisothiazole-2,2-dioxide
  参考文献：
  名称：

  基于碳自由基加成乙醛肟醚的不对称合成α-氨基酸

  摘要：

  报道了基于非对映选择性碳自由基加成乙醛酸亚胺衍生物的α-氨基酸的首次不对称合成。在25°C下，由i-PrI，Bu（3）SnH和Et（3）B在CH（2）Cl（2）中生成的异丙基向非手性乙醛酸肟醚1的区域选择性地在亚氨基上进行。肟醚基的碳原子可得到极佳的C-异丙基化产物2收率。乙醛肟肟1和醛肟醚4的竞争反应表明，乙醛肟肟醚对亲核碳自由基的反应性增强了相邻的吸电子取代基的结构。因此，与未活化的醛肟醚4相反，即使在-78℃下，向乙醛氧基肟醚1的烷基加成也顺利进行。通过使用Oppolzer的樟脑素作为手性助剂，可以实现对乙醛酸肟醚碳自由基加成的高度立体控制。樟脑素衍生物6与异丙基的甲炔基自由基介导的反应在-78℃下得到C-异丙基化产物的96：4非对映异构体混合物7a。通过用Mo（CO）（6）处理还原去除主要的非对映异构体（R）-7a的苄氧基，然后通过标准水解去除sultam助剂，得到对映体纯的D-缬氨酸（R）-

  DOI：

  10.1021/jo991353n
• 作为产物：
  描述：

  苄氧基胺盐酸盐 在 4-二甲氨基吡啶 、 sodium acetate 、 N,N'-二环己基碳二亚胺 作用下， 以 甲醇 、 二氯甲烷 、 水 为溶剂， 生成 methyl E-2-(benzyloxyimino)ethanate
  参考文献：
  名称：

  Discovery of potent, selective 4-fluoroproline-based thrombin inhibitors with improved metabolic stability

  摘要：

  Previous reports from our laboratories described potent tripeptide thrombin inhibitors which incorporate heterocycle-substituted chlorophenyl groups in the PI position. Using these as lead compounds for further optimization, we identified sites of metabolism and designed analogs with 4-fluoroproline in P2 and cyclopropane-containing side chains in P3 as an approach to reducing metabolism and improving their oral pharmacokinetic performance. The large (300-fold) difference in potency between analogs containing (4R)- and (4S)-4-fluoroproline was rationalized by analyzing inhibitor-enzyme interactions in crystal structures of related compounds and by molecular modeling which indicated that the more potent (4R)-4-fluoroproline isomer stabilizes a proline ring conformation that is preferred for binding to the enzyme. An optimal compound from this work, 41, exhibits high potency in a coagulation assay in human plasma (2xAPTT = 190 nM), excellent selectivity versus the digestive enzyme trypsin (K-i = 3300 nM), and excellent oral bioavailability in dogs with moderate clearance (F = 100%, CL = 12 mL/min/kg). (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2006.06.040

文献信息

• A Metathesis-Based Approach to the Synthesis of 2-Pyridones and Pyridines
  作者：Timothy J. Donohoe、Lisa P. Fishlock、Panayiotis A. Procopiou

  DOI：10.1021/ol702684d

  日期：2008.1.1

  intermediates, which are in the correct oxidation state to undergo a base-induced elimination to reveal the aromatic 2-pyridone. This mild and novel approach to six-membered heteroaromatic compounds then provides access to a wide variety of substituted pyridines in excellent overall yield.

  闭环复分解反应已成功地用于形成一系列二氢吡啶酮中间体，这些中间体处于正确的氧化态，可以进行碱诱导的消除反应，从而揭示出芳香族的2-吡啶酮。然后，这种温和新颖的六元杂芳族化合物方法可提供优异的总收率，可用于各种取代的吡啶。
• Indium mediated allylation of glyoxylate oxime ethers, esters and cyanoformates
  作者：Dougal J. Ritson、Russell J. Cox、John Berge

  DOI：10.1039/b402764g

  日期：——

  An indium mediated procedure has been developed for the allylation of activated O-functionalised oximes and nitriles as exemplified by a variety of glyoxylate derivatives. This method gives the corresponding free (or protected) amine in a one pot-process. The method is regiospecific and is carried out under remarkably mild conditions so that even oxime esters can be subjected to the typical reaction conditions.

  已开发出一种铟介导的方法，用于活化的O-官能化肟和腈的烯丙基化，如多种甘油酸衍生物的实例所示。该方法可在一步反应中获得相应的自由（或保护）胺。该方法具有区域选择性，并在非常温和的条件下进行，因此即使是肟酯也可以承受典型的反应条件。
• Reactions of Alkyl Radicals with Oxime Ether: One-Pot Synthesis of α-Amino Acids
  作者：Hideto Miyabe、Masafumi Ueda、Naoko Yoshioka、Kumiko Yamakawa、Takeaki Naito

  DOI：10.1016/s0040-4020(00)00119-8

  日期：2000.4

  addition of water-resistant carbon radicals to glyoxylic oxime ether provided a new method for the one-pot synthesis of α-amino acids via a carbon–carbon bond formation. The reaction of 2-hydroxy-2-methoxyacetic acid methyl ester with benzyloxyamine and an alkyl radical gave the protected α-amino acids via the stannyl radical-mediated reaction. In the absence of Bu3SnH, the predominant formation of the

  在乙醛酸肟醚中添加耐水的碳自由基为通过碳-碳键形成一锅法合成α-氨基酸提供了一种新方法。2-羟基-2-甲氧基乙酸甲酯与苄氧基胺和烷基的反应通过苯乙烯基自由基介导的反应得到了被保护的α-氨基酸。在不存在Bu 3 SnH的情况下，通过在沸腾的甲苯中使用RI和Et 3 B，也观察到主要形成所需的烷基化产物。Et 2 Zn和Et 3 B可以充当这些自由基反应的引发剂。
• Intermolecular alkyl radical addition to the carbon-nitrogen double bond of oxime ethers and hydrazones
  作者：Hideto Miyabe、Ryouhei Shibata、Masato Sangawa、Chikage Ushiro、Takeaki Naito

  DOI：10.1016/s0040-4020(98)00706-6

  日期：1998.9

  Intermolecular carbon radical addition to the carbon-nitrogen double bond of oxime ethers and hydrazones was studied. The reaction of unactivated aldoxime ethers proceeded smoothly in the presence of BF3·OEt2 to give the alkylated products in high yields via the free radical-mediated carbon-carbon bond-forming process.

  研究了肟醚和的碳-氮双键的分子间碳原子加成反应。未活化的醛肟醚的反应在BF 3 ·OEt 2的存在下顺利进行，通过自由基介导的碳-碳键形成过程以高收率得到烷基化产物。
• Diastereoselective addition of sugar radicals to camphorsultam glyoxilic oxime ether: a route toward C-glycosylthreonine and allothreonine
  作者：Nicolas Bragnier、Regis Guillot、Marie-Christine Scherrmann

  DOI：10.1039/b910050d

  日期：——

  C-glucosyl, mannosyl and galactosyl 2-iodopropane, readily obtained from the corresponding C-glycosyl ketones, were coupled with (+)- or (−)-camphorsultam glyoxylic oxime ether with diastereoselectivity ranging from 70:30 to 80:20. C-glucosyl allothreonine was obtained by cleavage of the camphorsultam moiety.

  C-葡萄糖基、甘露糖基和半乳糖基2-碘丙烷很容易从相应的C-糖基酮获得，与(+)-或(-)-樟脑磺内酰胺乙醛酸肟醚偶联，非对映选择性范围为70:30至80:20。 C-葡萄糖基别苏氨酸通过樟脑磺内酰胺部分的裂解获得。