(2S,3R,4S,5R)-trimethyl 5-(4-methoxyphenyl)pyrrolidine-2,3,4-tricarboxylate

• 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,5R)-trimethyl 5-(4-methoxyphenyl)pyrrolidine-2,3,4-tricarboxylate
• 英文别名: trimethyl (2S,3R,4S,5R)-5-(4-methoxyphenyl)pyrrolidine-2,3,4-tricarboxylate；(2S,3R,4S,5R)-2,3,4-tri(carbomethoxy)-5-(4-methoxyphenyl)pyrrolidine；(2S,3R,4R,5R)-2,3,4-tricarbomethoxy-5-(4-methoxyphenyl)pyrrolidine；(2S,3R,4S,5R)-2,3,4-tricarbomethoxy-5-(4-methoxyphenyl)pyrrolidine；trimethyl 5-(4-methoxyphenyl)pyrrolidine-2,3,4-tricarboxylate
• 化学式: C₁₇H₂₁NO₇
• 分子量: 351.356
• InChiKey: LULKGQUUVWSKHX-CRWXNKLISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  25
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  100
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  (2S,5R,6S,8R,9R)-5,6-diphenyl-7(R)-(p-methoxyphenyl)-8,9-dicarbomethoxy-1-aza-4-oxabicyclo<4.3.0>nonan-3-one 在 lead(IV) acetate 、 盐酸 作用下， 反应 2.17h， 生成 (2S,3R,4S,5R)-trimethyl 5-(4-methoxyphenyl)pyrrolidine-2,3,4-tricarboxylate
  参考文献：
  名称：

  Asymmetric [1,3]-dipolar cycloaddition reactions: synthesis of highly substituted proline derivatives

  摘要：

  The asymmetric [1,3]-dipolar cycloaddition reactions of azomethine ylides derived from (5R,6S)-2,3,5,6-tetrahydro-5,6-diphenyl-1,4-oxazin-2-one with various aldehydes and dimethyl maleate is described. The reactions prove to be highly endo-selective, installing three contiguous stereogenic centers in the newly formed five-membered ring with essentially complete stereochemical control. In the case of aldehydes higher than formaldehyde, a fourth stereogenic center is created; in most cases, poor stereoselectivity is observed at this center; the diastereomers formed in these cases can be separated by chromatography and separately converted into the amino acids. The bicyclic dipolar adducts can be cleaved with either catalytic hydrogenolysis or hydrolytic ring opening, esterification, and lead tetraacetate removal of the chiral auxiliary.

  DOI：

  10.1021/jo00050a029

文献信息

• Bifunctional AgOAc-Catalyzed Asymmetric [3 + 2] Cycloaddition of Azomethine Ylides
  作者：Wei Zeng、Yong-Gui Zhou

  DOI：10.1021/ol0520370

  日期：2005.10.1

  [reaction: see text] A bifunctional AgOAc-catalyzed asymmetric cycloaddition of azomethine ylides with electronic-deficient alkenes was developed using ferrocenyloxazoline-derived N,P ligands. The reactive metal-bound azomethine ylide dipole is formed by the deprotonation with acetate, and extra base is not necessary. The reactions proceed with high enantioselectivity. This method provides an efficient

  [反应：见正文]使用二茂铁基恶唑啉衍生的N，P配体开发了双官能AgOAc催化的偶氮甲亚胺与电子缺陷烯烃的不对称环加成反应。通过与乙酸盐的去质子化反应，与反应性金属结合的偶氮甲碱叶立德偶极子形成，并且不需要额外的碱。反应以高对映选择性进行。该方法提供了制备旋光吡咯烷衍生物的有效且方便的途径。
• Chiral ferrocenyl P,S-ligands for highly efficient copper-catalyzed asymmetric [3+2] cycloaddition of azomethine ylides
  作者：Fu-Zhong Han、Sai-Bo Yu、Cheng Zhang、Xiang-Ping Hu

  DOI：10.1016/j.tet.2015.01.003

  日期：2016.5

  on benzimidazole and imidazole backbones have been prepared from Ugi's amine through a three-step transformation. These ligands were successfully employed in the Cu-catalyzed asymmetric [3+2] cycloaddition of azomethine ylides with various electron-deficient olefins, giving the corresponding cycloadducts in high endo-selectivities and excellent enantioselectivities (up to 99% ee).

  通过三步转化，由乌吉的胺制备了一系列基于苯并咪唑和咪唑骨架的手性二茂铁基P，S-配体。这些配体已成功地用于铜催化的偶氮甲亚胺与各种缺电子的烯烃的不对称[3 + 2]环加成中，从而以较高的内选择性和出色的对映选择性（高达99％ee）得到相应的环加合物。
• 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。
• Asymmetric [3+2] Cycloaddition of Azomethine Ylides Catalyzed by Silver(I) Triflate with a Chiral Bipyrrolidine-Derived Phosphine Ligand
  作者：Zhen-Jiang Xu、Chi-Ming Che、Xin Gu、Vanessa Lo

  DOI：10.1055/s-0032-1316779

  日期：——

  bipyrrolidine-derived phosphine ligands L1 and L2 were synthesized. The ‘AgOTf + L1’ protocol catalyzes the asymmetric [3+2] cycloaddition of azomethine ylides with alkenes to give highly substituted pyrrolidines in good yields (up to 90%) with moderate to high diastereoselectivities (up to >19:1 dr) and enantioselectivities (up to 76%). Two novel chiral bipyrrolidine-derived phosphine ligands L1 and L2 were synthesized

  摘要 合成了两个新颖的手性联吡咯烷衍生的膦配体L1和L2。“ AgOTf + L1 ”方案可催化偶氮甲亚胺与烯烃的不对称[3 + 2]环加成反应，以高收率（高达90％），中等至高非对映选择性（高达> 19：1 dr）提供高度取代的吡咯烷。对映选择性（高达76％）。 合成了两个新颖的手性联吡咯烷衍生的膦配体L1和L2。“ AgOTf + L1 ”方案可催化偶氮甲亚胺与烯烃的不对称[3 + 2]环加成反应，以高收率（高达90％），中等至高非对映选择性（高达> 19：1 dr）提供高度取代的吡咯烷。对映选择性（高达76％）。
• Hydrogen-Bonding Directed Reversal of Enantioselectivity
  作者：Wei Zeng、Guo-Ying Chen、Yong-Gui Zhou、Yu-Xue Li

  DOI：10.1021/ja067346f

  日期：2007.1.1

  successful stereochemical reversal was achieved in AgOAc catalyzed [3+2] cycloaddition by the formation of hydrogen bonding between ligand and reactant. This strategy provides an efficient and convenient route to prepare both enantiomers of a chiral compound. DFT studies proposed a reasonable mechanism of the reversal of the enantioselectivity; hydrogen bonding changed the transition state. The strategy

  通过在配体和反应物之间形成氢键，在 AgOAc 催化的 [3+2] 环加成反应中实现了成功的立体化学逆转。该策略提供了一种有效且方便的途径来制备手性化合物的两种对映异构体。DFT 研究提出了对映选择性逆转的合理机制；氢键改变了过渡态。该策略可为配体设计提供一些有用的提示。