methyl N-p-chlorobenzylidene(phenyl)glycinate | 75984-69-9

• 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 N-p-chlorobenzylidene(phenyl)glycinate
• 英文别名: 4-ClC6H4CHNCH(Ph)CO2Me；Methyl 2-{[(4-chlorophenyl)methylene]amino}-2-phenylacetate；methyl 2-[(4-chlorophenyl)methylideneamino]-2-phenylacetate
• CAS: 75984-69-9
• 化学式: C₁₆H₁₄ClNO₂
• 分子量: 287.746
• InChiKey: AYZZZYYVDFDSOS-UHFFFAOYSA-N

物化性质

• 沸点：
  384.1±42.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl N-p-chlorobenzylidene(phenyl)glycinate 在 盐酸 、 四丁基氯化铵 、 水 、 potassium carbonate 、 potassium hydroxide 作用下， 以 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 98.0h， 生成 苯丙氨酸,a-苯基-,甲基酯
  参考文献：
  名称：

  NH₂ As a Directing Group: From the Cyclopalladation of Amino Esters to the Preparation of Benzolactams by Palladium(II)-Catalyzed Carbonylation of N-Unprotected Arylethylamines

  摘要：

  An unusual NH2-directed Pd(II)-catalyzed carbonylation of quaternary aromatic alpha-amino esters to yield benzolactams has been developed. The steric hindrance around the amino group is pivotal for the success of the process. The stoichiometric cyclometalation of a variety amino esters has been studied in order to evaluate the influence of the different variables (size of the metallacycle, aromatic ring substituents, and steric bulk) in the process, and a complete kinetico-mechanistic study of the cyclopalladation process has been carried out. The experimental results indicate that the full substitution of the carbon in the alpha position of the amino esters plays an important role in their cyclopalladation reaction. The reaction shows a strong bias toward six-membered lactams over the five-membered analogues, which can be explained by a greater reactivity of the six-membered palladacycles.

  DOI：

  10.1021/om301140t
• 作为产物：
  描述：

  2-氨基-2-苯基乙酸 在 氯化亚砜 、 magnesium sulfate 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 methyl N-p-chlorobenzylidene(phenyl)glycinate
  参考文献：
  名称：

  Duhamel, Lucette; Plaquevent, Jean-Christophe, Bulletin de la Societe Chimique de France, 1982, vol. 2, # 1-2, p. 75 - 83

  摘要：

  DOI：

文献信息

• Synergistic Cu/Pd Catalysis for Enantioselective Allylic Alkylation of Aldimine Esters: Access to α,α-Disubstituted α-Amino Acids
  作者：Liang Wei、Shi-Ming Xu、Qiao Zhu、Chao Che、Chun-Jiang Wang

  DOI：10.1002/anie.201707019

  日期：2017.9.25

  Double duty: An enantioselective allylic alkylation of aldimine esters has been developed by using a synergistic Cu/Pd catalyst system. This strategy provides access to nonproteinogenic α,α-disubstituted α-amino acids in high yield with excellent enantioselectivity. The more challenging double allylic alkylation of glycinate-derived imine esters was also be realized. LG=leaving group.

  双重职责：通过使用协同的Cu / Pd催化剂体系，开发了醛亚胺酯的对映选择性烯丙基烷基化反应。该策略提供了以优异的对映选择性高产率获得非蛋白原性的α，α-二取代的α-氨基酸的途径。还实现了更具挑战性的甘氨酸衍生的亚胺酯的双烯丙基烷基化。LG =离开小组。
• Stereodivergent synthesis of C-glycosamino acids via Pd/Cu dual catalysis
  作者：Xiaoxiao Yan、Feng Feng、Lin Zhou、Linrong Chen、Shouchu Tang、Jian Liu、Feng Cai、Xiaolei Wang

  DOI：10.1007/s11426-020-9930-7

  日期：2021.4

  stereodivergent synthesis of C-glycosamino acids via Pd/Cu dual catalysis and found a suitable system to resolve many challenges, such as the tolerance towards the density of functional groups, the variability of the anomeric position, the compatibility of appropriate catalyst combinations, the regioselectivity of nucleophiles, and the match/mismatch problems between chiral substrates and chiral ligand-metal

  在此，我们报道了通过 Pd/Cu 双催化立体发散合成 C-糖氨基酸，并找到了一个合适的系统来解决许多挑战，例如对官能团密度的耐受性、异头位置的可变性、适当的相容性催化剂组合、亲核试剂的区域选择性以及手性底物与手性配体-金属配合物之间的匹配/错配问题。该方法能够以良好的收率有效地制备一系列具有两个连续立体中心的非天然C-糖氨基酸骨架，并具有优异的非对映选择性。从这个关键的前体，各种 C-糖氨基酸衍生物已经得到了不同程度的实现。易于制备的 C-糖氨基酸杂化物将满足开发新分子实体以发现新药物和材料的日益增长的需求。C-糖氨基酸的这种立体发散合成将在不久的将来进一步加速对其结构特征、作用方式和潜在生物学应用的研究。
• Straightforward and Highly Stereoselective Synthesis of 3,3,4-Trifluoropyrrolidines Involving 1,3-Dipolar Cycloaddition with 2,3,3-Trifluoroacrylate
  作者：Shigeyuki Yamada、Masao Higashi、Tsutomu Konno、Takashi Ishihara

  DOI：10.1002/ejoc.201600837

  日期：2016.9

  lithium diisopropylamide, took place smoothly to give the corresponding 1,3-dipolar cycloadducts, fluorine-containing pyrrolidines, in good yields and with high diastereoselectivities (>95:<5). When the fluorinated acrylate bore a chiral auxiliary as a substituent, for instance (l)-(–)-menthyl ester, the 1,3-dipolar cycloaddition reaction was found to give the corresponding fluorinated pyrrolidine derivatives

  2,3,3-三氟丙烯酸苄酯与用二异丙基氨基锂处理亚氨基酯产生的偶氮甲碱叶立德的反应顺利进行，得到相应的1,3-偶极环加合物，含氟吡咯烷，收率良好，具有高非对映选择性 (>95:<5)。当氟化丙烯酸酯带有手性助剂作为取代基时，例如 (l)-(-)-薄荷酯，发现 1,3-偶极环加成反应不仅以非对映选择性而且以非对映选择性得到相应的氟化吡咯烷衍生物对映选择性方式。
• Catalytic Asymmetric Benzylation of Azomethine Ylides Enabled by Synergistic Lewis Acid/Palladium Catalysis
  作者：Xin Chang、Jing-Di Ran、Xue-Tao Liu、Chun-Jiang Wang

  DOI：10.1021/acs.orglett.2c00865

  日期：2022.4.8

  synergistic chiral Lewis acid/achiral Pd catalyst system was successfully applied in the enantioselective benzylation of various imine esters, giving a range of α-benzyl-substituted α-amino acid derivatives in satisfactory yield with excellent enantioselectivity. It is worth noting that this strategy exhibits good tolerance for bicyclic and monocyclic benzylic electrophiles. Furthermore, the utility of this

  协同手性路易斯酸/非手性钯催化剂体系成功应用于各种亚胺酯的对映选择性苄基化反应，得到一系列α-苄基取代的α-氨基酸衍生物，收率令人满意，对映选择性优异。值得注意的是，该策略对双环和单环苄基亲电试剂具有良好的耐受性。此外，通过方便制备对映体富集的抗高血压药物 α-甲基-l-多巴，证明了该合成方案的实用性。
• Amine‐Directed Palladium‐Catalyzed C−H Halogenation of Phenylalanine Derivatives
  作者：Alexia Ville、Julien Annibaletto、Sébastien Coufourier、Christophe Hoarau、Rodolphe Tamion、Guillaume Journot、Cédric Schneider、Jean‐François Brière

  DOI：10.1002/chem.202102411

  日期：2021.10.7

  efficient primary-amine-directed, palladium-catalyzed C−H halogenation (X=I, Br, Cl) of phenylalanine derivatives is reported on a range of quaternary amino acid (AA) derivatives thanks to suitable conditions employing trifluoroacetic acid as additive. The extension of this original native functionality-directed ortho-selective halogenation was even demonstrated with the more challenging native phenylalanine

  由于采用三氟乙酸作为添加剂的合适条件，在一系列季氨基酸 (AA) 衍生物上报道了苯丙氨酸衍生物的有效伯胺导向、钯催化的 C−H 卤化 (X=I, Br, Cl)。这种原始的天然官能团导向的邻位选择性卤化的扩展甚至用更具挑战性的天然苯丙氨酸作为叔 AA 得到了证明。