(2S,3R,4S,5S)-methyl 3-(4-chlorophenyl)-4-nitro-5-phenylpyrrolidine-2-carboxylate | 1223020-41-4

• 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: (2S,3R,4S,5S)-methyl 3-(4-chlorophenyl)-4-nitro-5-phenylpyrrolidine-2-carboxylate
• 英文别名: methyl (2S,3R,4S,5S)-3-(4-chlorophenyl)-4-nitro-5-phenylpyrrolidine-2-carboxylate
• CAS: 1223020-41-4
• 化学式: C₁₈H₁₇ClN₂O₄
• 分子量: 360.797
• InChiKey: XFQNOSFLESSKIV-QZWWFDLISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  84.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  1-(4-氯苯基)-2-硝基乙烯 、 [(苯基甲亚基)氨基]乙酸甲酯 在 silver trifluoromethanesulfonate 、 三苯基膦 作用下， 生成 (2S,3R,4S,5S)-methyl 3-(4-chlorophenyl)-4-nitro-5-phenylpyrrolidine-2-carboxylate
  参考文献：
  名称：

  高对映选择性铜/亚磷酰胺-硫醚催化的偶氮亚胺叶立德和硝基烯烃的非对映体1,3-偶极环加成反应

  摘要：

  与通过简单地在一对对映异构体或假对映异构体手性催化剂之间进行选择而能够获得手性产物的任何对映异构体的大量催化系统相反，几乎没有类似的有效方案可用于合成带有多个立体中心且能完全控制手性的化合物。绝对和相对立体化学构型。在这里，我们报道了我们先前开发的模块化亚磷酰胺-硫醚配体在铜催化的非对映异构体不对称的1,3-偶极环加成反应中的亚甲亚胺烷基化物和硝基烯烃的应用。我们的催化系统可实现广泛的底物范围，出色的立体化学控制和高反应效率。

  DOI：

  10.1002/chem.201705301

文献信息

• Brucine Diol–Copper-Catalyzed Asymmetric Synthesis of <i>endo</i>-Pyrrolidines: The Mechanistic Dichotomy of Imino Esters
  作者：Jian-Yuan Li、Hun Young Kim、Kyungsoo Oh

  DOI：10.1021/acs.orglett.5b00277

  日期：2015.3.6

  reaction pathways. A concerted endo-selective [3 + 2]-cycloaddition pathway is developed for the reaction of methyl imino ester, whereas endo-pyrrolidines with an opposite absolute stereochemical outcome are prepared by using the stepwise reaction pathway of tert-butyl imino ester. The development of catalyst- and substrate-controlled stereodivergent approaches highlights the inherent substrate–catalyst

  通过使用催化剂和底物控制的反应途径描述了吡咯烷的对映异构和非对映异构方法。建立了协同的内选择性[3 + 2]-环加成途径用于甲基亚氨基酯的反应，而通过使用叔丁基亚氨基酯的逐步反应途径制备了具有相反的绝对立体化学结果的内吡咯烷酮。催化剂和底物控制的立体发散剂方法的发展突出了金属化的偶氮甲碱的[3 + 2]-环加成反应中固有的底物-催化剂相互作用。
• Bifunctional AgOAc/ThioClickFerrophos catalyzed asymmetric 1,3-dipolar cycloaddition reaction of azomethine ylides to nitroalkenes
  作者：Midori Kimura、Yukiko Matsuda、Akihiro Koizumi、Chihiro Tokumitsu、Yuichiro Tokoro、Shin-ichi Fukuzawa

  DOI：10.1016/j.tet.2015.08.002

  日期：2016.5

  AgOAc/ThioClickFerrophos (TCF) complex catalyzed the 1,3-dipolar cycloaddition of azomethine ylides (glycine imino ester) to nitroalkenes. The corresponding endo-cycloadducts (88:12–98:2 endo/exo) were afforded in good yields with high enantioselectivities, up to 98% ee, without addition of external amine. AgOAc/TCF works as a bifunctional (Lewis acid and base) catalyst.

  AgOAc / ThioClickFerrophos（TCF）络合物催化偶氮甲亚胺（甘氨酸亚氨基酯）与硝基烯烃的1,3-偶极环加成反应。相应的内切-cycloadducts（88：12-98：2内型/外型）在具有高对映选择性良好的产率，高达98％ee值被得到，不添加外部胺。AgOAc / TCF可作为双功能（路易斯酸和碱）催化剂。
• Stereocontrolled Synthesis of Highly Substituted Proline Esters via [3 + 2] Cycloaddition between N-Metalated Azomethine Ylides and Nitroalkenes. Origins of the Metal Effect on the Stereochemical Outcome
  作者：Mirari Ayerbe、Ana Arrieta、Fernando P. Cossío、Anthony Linden

  DOI：10.1021/jo971212q

  日期：1998.3.1

  The [3 + 2] cycloaddition reaction between several N-metalated azomethine ylides and nitroalkenes has been studied using AgOAc and LiClO4 as metalating reagents in the presence of triethylamine. The reaction is found to be very versatile and can be extended to homochiral nitroalkenes. In general, lithium and silver salts promote preferential formation of the endo and exo cycloadducts, respectively. The presence of a phenol moiety induces a shift toward the exo-cycloadduct even when lithium is used. A model based upon the experimental results obtained and SCF-MO calculations is proposed to explain the variable stereochemical outcome of these reactions.
• Chiral Bis(imidazolidine)pyridine−Cu(OTf)₂: Catalytic Asymmetric Endo-Selective [3 + 2] Cycloaddition of Imino Esters with Nitroalkenes
  作者：Takayoshi Arai、Asami Mishiro、Naota Yokoyama、Kuniko Suzuki、Hiroyasu Sato

  DOI：10.1021/ja100265j

  日期：2010.4.21

  The novel C-2-symmetric bis(imidazolidine)pyridine (PyBidine) ligand was easily synthesized in a single condensation of 2,6-pyridyl aldehyde and optically active (S,S)diphenylethylenediamine. In the C-2-symmetric PyBidine-Cu(OTf)(2) complex, imidazolidine rings act as "chiral fences" to shield the first and third quadrants. Use of the PyBidine-Cu(OTf)(2) complex as a catalyst enabled the highly endo-selective reaction of imino esters and nitroalkenes to give the adducts in up to 99% ee.
• A Highly Enantioselective Copper/Phosphoramidite-Thioether-Catalyzed Diastereodivergent 1,3-Dipolar Cycloaddition of Azomethine Ylides and Nitroalkenes
  作者：Bin Feng、Jia-Rong Chen、Yun-Fang Yang、Bin Lu、Wen-Jing Xiao

  DOI：10.1002/chem.201705301

  日期：2018.2.1

  full control of the absolute and relative stereochemical configurations. Here, we report the application of our previously developed modular phosphoramidite‐thioether ligands for the copper‐catalyzed diastereodivergent asymmetric 1,3‐dipolar cycloaddition of azomethine ylides and nitroalkenes. Our catalytic system enables wide substrate scope, great stereochemical control, and high reaction efficiency

  与通过简单地在一对对映异构体或假对映异构体手性催化剂之间进行选择而能够获得手性产物的任何对映异构体的大量催化系统相反，几乎没有类似的有效方案可用于合成带有多个立体中心且能完全控制手性的化合物。绝对和相对立体化学构型。在这里，我们报道了我们先前开发的模块化亚磷酰胺-硫醚配体在铜催化的非对映异构体不对称的1,3-偶极环加成反应中的亚甲亚胺烷基化物和硝基烯烃的应用。我们的催化系统可实现广泛的底物范围，出色的立体化学控制和高反应效率。