methyl (E)-2-acetylamino-3-(4-chlorophenyl)-2-propenoate | 312300-60-0

• 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: methyl (E)-2-acetylamino-3-(4-chlorophenyl)-2-propenoate
• 英文别名: methyl (E)-2-acetamido-3-(4-chlorophenyl)prop-2-enoate
• CAS: 312300-60-0
• 化学式: C₁₂H₁₂ClNO₃
• 分子量: 253.685
• InChiKey: SZMVIMNGIUHOFW-YRNVUSSQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  55.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (E)-2-acetylamino-3-(4-chlorophenyl)-2-propenoate 在 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 (R)-(-)-2,2'-bis(diphenylphosphinoamino)-5,5'-(octamethylenedioxy)-1,10-biphenyl 作用下， 以 二氯甲烷 为溶剂， 20.0 ℃ 、303.99 kPa 条件下， 反应 20.0h， 以100%的产率得到methyl (S)-2-acetamido-3-(4-chlorophenyl)propanoate
  参考文献：
  名称：

  Synthesis of atropisomeric 5,5′-linked biphenyl bisaminophosphine ligands and their applications in asymmetric catalysis

  摘要：

  Atropisomeric 5,5'-linked biphenyl bisaminophosphine ligands 2 has been synthesized. The axial chirality of this type of ligands can be retained by macro ring strain produced from 5,5'-linkage of biphenyl even without 6,6'-substituents on biphenyls. The Rh complex of bisaminophosphine 2a as a catalyst is effectively working in the asymmetric hydrogenation of methyl (Z)-2-acetamido-3-arylacrylates, however, for hydrogenation of arylenamide, the low enantioselectivity was observed. When the ligands applied to Pd-catalyzed allylic alkylation, it is found that ligand 2b having a longer backbone linkage is a better ligand for enantioselection in the reaction. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2008.12.056
• 作为产物：
  描述：

  甲基2-乙酰氨基-3-(4-氯苯基)丙烯酸酯 在 二苯甲酮 作用下， 以 乙腈 为溶剂， 生成 methyl (E)-2-acetylamino-3-(4-chlorophenyl)-2-propenoate
  参考文献：
  名称：

  Spirochroman-2-on-4,1'-indan-7'-ol 的设计与合成及其在合成手性单次亚膦酸酯配体中的应用†

  摘要：

  报道了spirochroman-2-on-4,1'-indan-7'-ol (SCIOL)的设计和合成及其在合成手性单次亚膦酸酯配体中的应用。该合成采用串联双Friedel-Crafts反应/内酯化反应构建螺环骨架，经过6步得到了所需的外消旋SCIOL，总产率为44.5%。使用N-苄基辛可丁鎓氯化物进行包合拆分，可以以克级的良好收率获得光学 SCIOL。初步研究表明，相应的手性螺单次亚膦酸酯配体在铑催化的N-乙酰基脱氢氨基酯的不对称氢化反应中表现出较高的催化活性和对映选择性（高达94% ee）。这些结果凸显了 SCIOL 作为开发手性螺配体的有用框架的巨大潜力。

  DOI：

  10.1002/cjoc.202300319

文献信息

• Synthesis of Diastereomeric 1,4-Diphosphine Ligands Bearing Imidazolidin-2-one Backbone and Their Application in Rh(I)-Catalyzed Asymmetric Hydrogenation of Functionalized Olefins
  作者：Yong?Jian Zhang、Kee?Yong Kim、Jung?Hwan Park、Choong?Eui Song、Kyungae Lee、Myoung?Soo Lah、Sang-gi Lee

  DOI：10.1002/adsc.200404286

  日期：2005.3

  The diastereomeric 1,4-diphosphine ligands, (S,S,S,S)-1a, (R,S,S,R)-1b and (R,S,S,S)-1c, with the imidazolidin-2-one backbone were synthesized, and utilized for an investigation of the effects of backbone chirality on the enantioselectivity in the Rh(I)-catalyzed hydrogenation of various functionalized olefinic substrates. It was found that the catalytic efficiencies are largely dependent on the configurations

  非对映体1,4-二膦配体（S，S，S，S）-1a，（R，S，S，R）-1b和（R，S，S，S）-1c，含咪唑啉二-2合成一个骨架，并将其用于研究骨架手性对Rh（I）催化的各种官能化烯烃底物加氢中对映选择性的影响。已经发现，催化效率在很大程度上取决于α-碳到膦的构型。因此，伪c ^ 2 -symmetrical二膦，（- [R ，小号，小号，小号） - 1C，表明在基片，特别是在甲基α-的氢化的广谱的氢化优异的对映选择性（93.0-98.6％EES）（ñ -乙酰胺基）-β-芳基丙烯酸酯（95.3–97.0％ee）。但是，通过C 2对称的（R，S，S，R）-1b获得的对映选择性很大程度上取决于底物（19.8–97.3％ee）。配位体的铑配合物1a中具有（小号，小号，S，S）-构型显示了所有被检测底物的最低催化效率（0-84.8％ee）。
• Formation of Isoquinoline Deriva-tives by the Irradiation of N-Acetyl- a-dehydrophenylalanine Ethyl Ester and Its Derivatives
  作者：Tadamitsu Sakurai、Hideki Hoshina、Hitoshi Tsuru、Kanji Kubo、Tetsutaro Igarashi

  DOI：10.3987/com-00-8999

  日期：——
• Photo-stimulated Heterolysis of the C(=O)-O Bond in (Z)-N-Acetyl-a-dehydrophenylalanine Aryl Ester Derivatives
  作者：Tadamitsu Sakurai、Hideki Hoshina、Kentaro Nakayama、Tetsutaro Igarashi

  DOI：10.3987/com-02-9515

  日期：——
• Synthesis of atropisomeric 5,5′-linked biphenyl bisaminophosphine ligands and their applications in asymmetric catalysis
  作者：Yong Jian Zhang、Hao Wei、Wanbin Zhang

  DOI：10.1016/j.tet.2008.12.056

  日期：2009.2

  Atropisomeric 5,5'-linked biphenyl bisaminophosphine ligands 2 has been synthesized. The axial chirality of this type of ligands can be retained by macro ring strain produced from 5,5'-linkage of biphenyl even without 6,6'-substituents on biphenyls. The Rh complex of bisaminophosphine 2a as a catalyst is effectively working in the asymmetric hydrogenation of methyl (Z)-2-acetamido-3-arylacrylates, however, for hydrogenation of arylenamide, the low enantioselectivity was observed. When the ligands applied to Pd-catalyzed allylic alkylation, it is found that ligand 2b having a longer backbone linkage is a better ligand for enantioselection in the reaction. (C) 2008 Elsevier Ltd. All rights reserved.