methyl (1S,3R,3aS,6aR)-4,6-dioxo-3-(p-methoxyphenyl)-5-phenyl-octahydropyrrolo[3,4-c]pyrrole-1-carboxylate

• 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 (1S,3R,3aS,6aR)-4,6-dioxo-3-(p-methoxyphenyl)-5-phenyl-octahydropyrrolo[3,4-c]pyrrole-1-carboxylate
• 英文别名: methyl (1R,3S,3aR,6aS)-1-(4-methoxyphenyl)-4,6-dioxo-5-phenyl-2,3,3a,6a-tetrahydro-1H-pyrrolo[3,4-c]pyrrole-3-carboxylate
• 化学式: C₂₁H₂₀N₂O₅
• 分子量: 380.4
• InChiKey: VWOBFJMDKYIOJN-MHORFTMASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  28
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  84.9
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  4-甲氧基苯甲醛 在 tetrakis(acetonitrile)copper(I) perchlorate 、 magnesium sulfate 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 methyl (1S,3R,3aS,6aR)-4,6-dioxo-3-(p-methoxyphenyl)-5-phenyl-octahydropyrrolo[3,4-c]pyrrole-1-carboxylate
  参考文献：
  名称：

  CuI–Fesulphos complexes: efficient chiral catalysts for asymmetric 1,3-dipolar cycloaddition of azomethine ylides

  摘要：

  The Cu-I-Fesulphos catalyst system (<= 3 mol %) shows an excellent performance in the asymmetric 1,3-dipolar cycloaddition of azomethine ylides. High to very high levels of reactivity, endo/exo selectivity, and enantioselectivity ( 69->99% ee) are generally achieved with a very wide range of azomethine ylides and dipolarophiles. Based on experimental and computational studies data, a model that accounts for this high enantiocontrol is proposed. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.03.130

文献信息

• Highly Enantioselective Copper(I)−Fesulphos-Catalyzed 1,3-Dipolar Cycloaddition of Azomethine Ylides
  作者：Silvia Cabrera、Ramón Gómez Arrayás、Juan C. Carretero

  DOI：10.1021/ja0552186

  日期：2005.11.30

  The catalyst system formed by Cu(CH3CN)4ClO4 and the planar chiral P,S-ligand Fesulphos behaves as a very efficient chiral Lewis acid in the catalytic asymmetric 1,3-dipolar cycloaddition of azomethine ylides. This catalyst shows a remarkable reactivity at low catalyst loading (0.5-3 mol %), affording in good yields the endo adducts with exceptional levels of enantioselectivity (up to >99% ee). This

  由 Cu(CH3CN)4ClO4 和平面手性 P,S-配体 Fesulphos 形成的催化剂体系在催化偶氮甲碱叶立德的不对称 1,3-偶极环加成反应中充当非常有效的手性路易斯酸。该催化剂在低催化剂负载量（0.5-3 mol%）下表现出显着的反应性，以良好的收率提供具有特殊水平对映选择性（高达> 99% ee）的内加合物。这种催化不对称过程在偶氮甲碱和亲偶极体取代方面具有广泛的结构范围。报道了与酮亚胺衍生的偶氮甲碱的催化不对称 1,3-偶极环加成反应的第一个例子。
• AgOAc catalyzed asymmetric [3+2] cycloaddition of azomethine ylides with chiral ferrocene derived P,S ligands
  作者：Wei Zeng、Yong-Gui Zhou

  DOI：10.1016/j.tetlet.2007.04.101

  日期：2007.6

  Ferrocene derived P,S-heterodonor ligands were effectively used in AgOAc catalyzed asymmetric cycloaddition of azomethine ylides. The roles of planar chirality and electronic properties of the phosphorous substituents have been examined, and up to 93% ee was obtained.

  二茂铁衍生的P，S-杂配体配体可有效地用于AgOAc催化的甲亚胺基团的不对称环加成反应。已经检查了磷取代基的平面手性和电子性质的作用，并且获得了高达93％的ee。
• Synthesis of Polymer-Supported Fesulphos Ligands and their Application in Asymmetric Catalysis
  作者：Belén Martín-Matute、Susana Isabel Pereira、Eduardo Peña-Cabrera、Javier Adrio、Artur M. S. Silva、Juan C. Carretero

  DOI：10.1002/adsc.200600647

  日期：2007.7.2

  Fesulphos-based chiral ligands and their immobilization on a polystyrene support is described. These supported chiral ligands act as very efficient catalysts in 1,3-dipolar cycloaddition and allylic substitution reactions providing the products with excellent enantioselectivities (91 to >99 % ee). Filtration of the catalyst from the reaction mixtures allows simple product isolation. The polymer-supported Cu complex

  描述了两个基于Fesulphos的手性配体的合成及其在聚苯乙烯载体上的固定。这些负载的手性配体在1,3-偶极环加成反应和烯丙基取代反应中起非常有效的催化剂的作用，使产物具有出色的对映选择性（91至> 99％ee）。从反应混合物中过滤催化剂可以简单地分离产物。手性配体PS- 8的聚合物负载的Cu配合物可以在1，3-偶极环加成反应中无需进一步添加铜盐的情况下进行再循环。
• Catalysis of a 1,3-dipolar reaction by distorted DNA incorporating a heterobimetallic platinum(<scp>ii</scp>) and copper(<scp>ii</scp>) complex
  作者：Iván Rivilla、Abel de Cózar、Thomas Schäfer、Frank J. Hernandez、Alexander M. Bittner、Aitziber Eleta-Lopez、Ali Aboudzadeh、José I. Santos、José I. Miranda、Fernando P. Cossío

  DOI：10.1039/c7sc02311a

  日期：——

  A novel catalytic system based on covalently modified DNA is described. This catalyst promotes 1,3-dipolar reactions between azomethine ylides and maleimides. The catalytic system is based on the distortion of the double helix of DNA by means of the formation of Pt(II) adducts with guanine units. This distortion, similar to that generated in the interaction of DNA with platinum chemotherapeutic drugs

  描述了一种基于共价修饰的DNA的新型催化系统。该催化剂促进了甲亚胺烷基化物和马来酰亚胺之间的1，3-偶极反应。催化系统基于DNA的双螺旋的变形，该结构是通过形成带有鸟嘌呤单元的Pt（II）加合物来实现的。这种畸变类似于DNA与铂化学治疗药物相互作用中产生的畸变，产生了可以容纳N-金属化的偶氮甲亚胺酰化物的活性位点。所提出的反应机理，基于QM（DFT）/ MM的计算，是与通向外消旋只形成热允许一致（但异步）[π4s+π2s]机制兼容内切-cycloadducts。
• Development of chiral metal amides as highly reactive catalysts for asymmetric [3 + 2] cycloadditions
  作者：Yasuhiro Yamashita、Susumu Yoshimoto、Mark J Dutton、Shū Kobayashi

  DOI：10.3762/bjoc.12.140

  日期：——

  Highly efficient catalytic asymmetric [3 + 2] cycloadditions using a chiral copper amide are reported. Compared with the chiral CuOTf/Et3N system, the CuHMDS system showed higher reactivity, and the desired reactions proceeded in high yields and high selectivities with catalyst loadings as low as 0.01 mol %.

  报道了使用手性铜酰胺的高效催化不对称[3 + 2]环加成反应。与手性CuOTf / Et3N体系相比，CuHMDS体系显示出更高的反应活性，所需的反应以高收率和高选择性进行，催化剂负载量低至0.01 mol％。