Ethyl α-(diethoxyphosphinyl)-α-(4-methoxyphenyl)acetate | 152302-86-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: Ethyl α-(diethoxyphosphinyl)-α-(4-methoxyphenyl)acetate
• 英文别名: (diethoxyphosphoryl)-4-methoxyphenylacetic acid ethyl ester；ethyl 2-(diethoxyphosphoryl)-2-(4-methoxyphenyl)acetate；triethyl 2-(4-methoxyphenyl)phosphonoacetate；Ethyl 2-diethoxyphosphoryl-2-(4-methoxyphenyl)acetate
• CAS: 152302-86-8
• 化学式: C₁₅H₂₃O₆P
• 分子量: 330.318
• InChiKey: XEPQYUVNSLFZMH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  22
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2-羟基-3-(2-苯基-2-氧代)乙基-1,4-萘醌 、 Ethyl α-(diethoxyphosphinyl)-α-(4-methoxyphenyl)acetate 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 lithium chloride 作用下， 以 乙腈 为溶剂， 反应 0.17h， 生成 2-[2-ethoxycarbonyl-2-(4-methoxy-phenyl)-vinyl]-pyrrolidine-1-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  一种基于烯丙基菌株设计构象受限的类似物的方法：合成具有丙烯酰胺结构的新型非竞争性NMDA受体拮抗剂。

  摘要：

  通过基于烯丙基菌株的方法设计了一系列的构象受限的米那普仑（一种弱的NMDA受体拮抗剂）类似物。构象分析研究表明确实发生了基于烯丙基菌株的构象限制，并且通过构象限制有效地提高了对NMDA受体的亲和力。

  DOI：

  10.1021/jm030226n
• 作为产物：
  描述：

  乙酯4-甲氧基苯并基甲酸盐 在 sodium tetrahydroborate 、 三溴化磷 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 3.25h， 生成 Ethyl α-(diethoxyphosphinyl)-α-(4-methoxyphenyl)acetate
  参考文献：
  名称：

  2-芳基取代肉桂酸酯的可靠和多功能合成

  摘要：

  2-芳基取代的膦酰基乙酸酯可以通过四步序列从各自的芳烃容易地合成。即使在涉及敏感部分时，成功的 Horner-Wadsworth-Emmons 烯化也可立体选择性地提供 2-芳基肉桂酸酯。

  DOI：

  10.1055/s-2006-942404

文献信息

• Oxidative Cyclization Reaction of 2-Aryl-Substituted Cinnamates To Form Phenanthrene Carboxylates by Using MoCl₅
  作者：Kathrin Wehming、Moritz Schubert、Gregor Schnakenburg、Siegfried R. Waldvogel

  DOI：10.1002/chem.201403442

  日期：2014.9.22

  The oxidative cyclization reaction of 2‐aryl cinnamates and derivatives thereof can be easily performed with MoCl5 as the oxidant. This powerful reagent allows oxidative coupling reactions for which other reagents fail. The best results are obtained when the 2‐phenyl substituent of the cinnamate is equipped with two methoxy groups. Even iodo moieties in the bay region of phenanthrene are tolerated

  以MoCl 5为氧化剂可以轻松地进行2-芳基肉桂酸酯及其衍生物的氧化环化反应。这种强大的试剂可进行其他试剂无法完成的氧化偶联反应。当肉桂酸酯的2-苯基取代基带有两个甲氧基时，可获得最佳结果。在反应条件下甚至菲的海湾区域中的碘部分也是被容许的。如果涉及萘基，则会发生骨架的重排，从而为高功能化的角芳烃提供了一条优雅的途径。证明了15种底物的环化反应，菲衍生物的分离产率高达99％。反应的广泛范围强调了MoCl 5和MoCl 5的有用性/ TiCl 4中的氧化偶合反应。
• Molybdenum Pentachloride Mediated Synthesis of Spirocyclic Compounds by Intramolecular Oxidative Coupling
  作者：Moritz Schubert、Kathrin Wehming、Anton Kehl、Martin Nieger、Gregor Schnakenburg、Roland Fröhlich、Dieter Schollmeyer、Siegfried R. Waldvogel

  DOI：10.1002/ejoc.201501384

  日期：2016.1

  The oxidative treatment of (m)ethyl 2-aryl cinnamates equipped with methoxy groups in position 4 of the phenyl moiety promote the formation of cyclohexadienone substructures. This dealkylative oxidative C–C coupling gives access to spirocyclic compounds and avoids the construction of the corresponding phenanthrenes. Furthermore, the transformation can be expanded to other spirocyclic systems.

  在苯基部分的 4 位带有甲氧基的（m）乙基 2-芳基肉桂酸酯的氧化处理促进了环己二烯酮亚结构的形成。这种脱烷基氧化性 C-C 偶联提供了获得螺环化合物的途径，并避免了相应菲的构建。此外，转化可以扩展到其他螺环系统。
• Copper(I) salt-mediated arylation of phosphinyl-stabilized carbanions and synthetic application to heterocyclic compounds
  作者：Toru Minami、Takeshi Isonaka、Yoshiharu Okada、Junji Ichikawa

  DOI：10.1021/jo00077a018

  日期：1993.12

  The copper-mediated reaction of phosphinyl-stabilized carbanions 2a-c with aryl halides 1a-i in DMF or HMPA produced (arylmethyl)phosphonates 3-11 in good yields. Similar treatment of N-(2-iodophenyl)- and N-(2-iodophenyl)-N-methyl-alpha-(diethoxyphosphinyl)acetamides (12 and 14) led to 2-[(diethoxyphosphinyl)methyl]benzoxazole (13) and 1-methyl-3-(diethoxyphosphinyl)oxindole (15) in 71 and 85% yields, respectively. 4-(Ethoxycarbonyl)-3,4-dihydroisoquinoline N-oxide (33) was synthesized by the reaction of ethyl alpha-(o-formylphenyl)acrylate (31), derived from 6 and paraformaldehyde,with hydroxylamine. The cycloaddition of 33 to olefins such as dimethyl maleate, methyl acrylate, and styrene was studied.
• Route to α-Aryl Phosphonoacetates: Useful Synthetic Precursors in the Horner–Wadsworth–Emmons Olefination
  作者：Kelsey F. VanGelder、Melinda Wang、Marisa C. Kozlowski

  DOI：10.1021/acs.joc.5b01887

  日期：2015.10.16

  A versatile and general catalytic strategy has been developed for the alpha-arylation of phosphonoacetates utilizing parallel microscale experimentation. These a-substituted phosphonoacetates are widely useful, notably as substrates in the Horner-Wadsworth-Emmons-type olefinations. However, the current routes to these products involve harsh conditions, limiting the variety of functionality. The reported method can be used with a variety of aryl chlorides and aryl bromides, including several heterocyclic examples.
• Minami Toru, Isonaka Takeshi, Okada Yoshiharu, Ichikawa Junji, J. Org. Chem, 58 (1993) N 25, S 7009-7015
  作者：Minami Toru, Isonaka Takeshi, Okada Yoshiharu, Ichikawa Junji

  DOI：——

  日期：——