(2S,3S,4R,5S)-methyl 5-(4-bromophenyl)-4-nitro-3-phenylpyrrolidine-2-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: (2S,3S,4R,5S)-methyl 5-(4-bromophenyl)-4-nitro-3-phenylpyrrolidine-2-carboxylate
• 英文别名: methyl (2S,3S,4R,5S)-5-(4-bromophenyl)-4-nitro-3-phenylpyrrolidine-2-carboxylate
• 化学式: C₁₈H₁₇BrN₂O₄
• 分子量: 405.248
• InChiKey: XFIHJNYQYDMGFE-LUKYLMHMSA-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：

  β-硝基苯乙烯 、 N-(4-bromobenzylidene)glycine methyl ester 在 (R,Sp)-ThioClickFerrophos 、 silver(I) acetate 作用下， 以 1,4-二氧六环 为溶剂， 反应 10.0h， 以51%的产率得到(2S,3R,4S,5S)-methyl 5-(4-bromophenyl)-4-nitro-3-phenylpyrrolidine-2-carboxylate
  参考文献：
  名称：

  双功能AgOAc / ThioClickFerrophos催化的偶氮甲亚胺基化物与硝基烯烃的不对称1,3-偶极环加成反应

  摘要：

  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。

  DOI：

  10.1016/j.tet.2015.08.002

文献信息

• Enantioselective Synthesis of exo-4-Nitroprolinates from Nitro­alkenes and Azomethine Ylides Catalyzed by Chiral Phosphor­amidite·Silver(I) or Copper(II) Complexes
  作者：José Sansano、Luis Castelló、Carmen Nájera、Olatz Larrañaga、Abel de Cózar、Fernando Cossío

  DOI：10.1055/s-0034-1380158

  日期：——

  procedures are complementary but silver catalysts are more versatile and less sensitive to sterically congested starting materials. Chiral complexes formed by privileged phosphoramidites derived from chiral binol and optically pure Davies’ amines, and copper(II) triflate, silver(I) triflate or silver(I) benzoate are excellent catalysts for the general 1,3-dipolar cycloaddition between nitroalkenes and azomethine

  摘要 由手性二元醇和光学纯的Davies胺衍生的特权亚磷酰胺与三氟甲磺酸铜（II），三氟甲磺酸银（I）或苯甲酸银（I）形成的手性络合物是硝基烯烃与苯甲酸酯之间一般1,3-偶极环加成反应的出色催化剂由α-氨基酸衍生的亚氨基酯生成的甲亚胺基亚胺。这三种方法可以在室温下进行，得到外-cycloadducts（4,5-反式-2,5-顺式-4- nitroprolinates）具有高非对映选择性和高对映选择性。通常，这三种方法是互补的，但银催化剂用途更广，对空间拥挤的起始原料不敏感。 由手性二元醇和光学纯的Davies胺衍生的特权亚磷酰胺与三氟甲磺酸铜（II），三氟甲磺酸银（I）或苯甲酸银（I）形成的手性络合物是硝基烯烃与苯甲酸酯之间一般1,3-偶极环加成反应的出色催化剂由α-氨基酸衍生的亚氨基酯生成的甲亚胺基亚胺。这三种方法可以在室温下进行，得到外-cycloadducts（4,5-反式-2,5-顺式-4-
• Efficient Diastereo- and Enantioselective Synthesis of<i>exo</i>-Nitroprolinates by 1,3-Dipolar Cycloadditions Catalyzed by Chiral Phosphoramidite⋅Silver(I) Complexes
  作者：Luis M. Castelló、Carmen Nájera、José M. Sansano、Olatz Larrañaga、Abel de Cózar、Fernando P. Cossío

  DOI：10.1002/adsc.201400563

  日期：2014.12.15

  AbstractChiral complexes formed by privileged phosphoramidites and silver triflate or silver benzoate are excellent catalysts for the general 1,3‐dipolar cycloaddition between azomethine ylides generated from α‐amino acid‐derived imino esters and nitroalkenes affording with high dr the exo‐cycloadducts 4,5‐trans‐2,5‐cis‐4‐nitroprolinates in high ee at room temperature. In general, better results are obtained using silver rather than copper(II) complexes. In many cases the exo‐cycloadducts can be obtained in enantiomerically pure form just after simple recrystallization. The mechanism and the justification of the experimentally observed stereodiscrimination of the process are supported by DFT calculations. These enantiomerically enriched exo‐nitroprolinates can be used as reagents for the synthesis of nitropiperidines, by ester reduction and ring expansion, which are inhibitors of farnesyltransferase.magnified image
• Phosphoramidite–Cu(OTf)₂ Complexes as Chiral Catalysts for 1,3-Dipolar Cycloaddition of Iminoesters and Nitroalkenes
  作者：Luis M. Castelló、Carmen Nájera、José M. Sansano、Olatz Larrañaga、Abel de Cózar、Fernando P. Cossío

  DOI：10.1021/ol4006618

  日期：2013.6.21

  Chiral complexes formed by phosphoramidites such as (S-a,R,R)-9 and Cu(OTf)(2) are excellent catalysts for the general 1,3-dipolar cycloaddition between azomethine ylides and nitroalkenes affording the corresponding tetrasubstituted proline esters mainly as exo-cycloadducts in high er at room temperature. The exo-cycloadducts can be obtained in enantiomerically pure form just after simple recrystallization. DFT calculations support the stereochemical results.
• A Highly Enantio- and Diastereoselective Cu-Catalyzed 1,3-Dipolar Cycloaddition of Azomethine Ylides with Nitroalkenes
  作者：Xiao-Xia Yan、Qian Peng、Yan Zhang、Kai Zhang、Wei Hong、Xue-Long Hou、Yun-Dong Wu

  DOI：10.1002/anie.200503672

  日期：2006.3.13
• 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。