ethyl (2S,3R)-3-formyl-2-(4-methoxyphenylamino)-pentanoate

• 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: ethyl (2S,3R)-3-formyl-2-(4-methoxyphenylamino)-pentanoate
• 英文别名: (2S,3R)-ethyl 3-formyl-2-(4-methoxyphenylamino)pentanoate；ethyl (2S,3R)-3-formyl-2-(p-methoxyphenylamino)pentanoate；ethyl (2S,3R)-3-formyl-2-(4-methoxyanilino)pentanoate
• 化学式: C₁₅H₂₁NO₄
• 分子量: 279.336
• InChiKey: DYCSJQDOBGQFHO-FZMZJTMJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  20
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  ethyl (4-methoxyphenylimino)acetate 、 正丁醛 在 1-(3,5-bis(trifluoromethyl)phenyl)-3-((3R,5S)-5-((tert-butyldiphenylsilyloxy)methyl)pyrrolidin-3-yl)thiourea 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 2.0h， 以93%的产率得到ethyl (2S,3R)-3-formyl-2-(4-methoxyphenylamino)-pentanoate
  参考文献：
  名称：

  4-氨基硫脲脯氨醇叔丁基二苯基甲硅烷基醚：手性仲胺-硫脲作为对映选择性反曼尼希反应的有机催化剂

  摘要：

  抗的-选择性曼尼希反应ñ - p -甲氧基苯基（PMP）与未改性的醛或酮-保护的α-iminoglyoxylate得到有效利用4-氨基硫脲脯氨醇催化叔-butyldiphenylsilyl醚。反应导致高收率（高达94％），出色的非对映异构和对映选择性（高达98％de和> 99％ee）的手性β-氨基羰基化合物。该研究首次证明，仲胺-硫脲手性有机催化剂可促进未修饰醛或酮与α-亚氨基乙醛酸酯的直接曼尼希型反应。

  DOI：

  10.1002/adsc.200900399

文献信息

• anti-Selective SMP-catalyzed direct asymmetric Mannich-type reactions: synthesis of functionalized amino acid derivatives
  作者：Armando Córdova、Carlos F Barbas

  DOI：10.1016/s0040-4039(02)01772-0

  日期：2002.10

  The first (S)-2-methoxymethylpyrrolidine (SMP)-catalyzed direct asymmetric Mannich-type reactions of unmodified aldehydes with N-PMP-protected α-imino ethyl glyoxylate are described. The reaction proceeded in a highly anti-selective manner (dr up to 19:1) with enantioselectivities between 74 and 92%.

  描述了未改性的醛与N -PMP保护的α-亚氨基乙基乙醛酸酯的第一（S）-2-甲氧基甲基吡咯烷（SMP）催化的直接不对称曼尼希型反应。反应以高度反选择性的方式（dr高达19：1）进行，对映选择性在74％至92％之间。
• Design of a C2-symmetric chiral pyrrolidine-based amino sulfonamide: application to anti-selective direct asymmetric Mannich reactions
  作者：Taichi Kano、Yoshio Hato、Keiji Maruoka

  DOI：10.1016/j.tetlet.2006.09.147

  日期：2006.11

  The anti-selective direct asymmetric Mannich reaction was found to be efficiently catalyzed by the novel pyrrolidine-based amino sulfonamide (R,R)-2 prepared from l-tartaric acid.

  所述抗-选择性直接不对称曼尼希反应被发现通过新的吡咯烷基氨基磺酰胺（被有效地催化- [R ，- [R ）- 2从1-酒石酸制备。
• Monolithic Silica Support for Immobilized Catalysis in Continuous Flow
  作者：M. Grace Russell、Cedrick Veryser、James F. Hunter、Rachel L. Beingessner、Timothy F. Jamison

  DOI：10.1002/adsc.201901185

  日期：2020.1.23

  reactors featuring immobilized catalysts are well‐precedented in continuous flow synthesis but can suffer from adverse pressure drops during use due to their small pore sizes and/or structural changes. Herein, we overcome this challenge with the synthesis of a structurally robust silica‐based monolith featuring pore sizes on the millimeter scale. The 3‐dimensional solid support structure is constructed

  具有固定化催化剂的整体式和填充床反应器在连续流合成中是先例，但由于其孔径小和/或结构变化，在使用过程中会遭受不利的压降。在本文中，我们通过合成孔径为毫米级的结构坚固的二氧化硅基整体材料克服了这一挑战。3维固体支撑结构由基于聚苯乙烯泡沫的模板构造而成，并具有可进行修饰以显示反应性催化剂的官能团手柄。在这里，我们用钯（0）进行加氢反应的功能化载体和改性的脯氨酸催化剂对醛的α官能化功能化。当在连续流动条件下使用时，两个反应器均显示出良好的活性和优异的催化寿命。
• A General Organocatalyst for Direct α-Functionalization of Aldehydes:  Stereoselective C−C, C−N, C−F, C−Br, and C−S Bond-Forming Reactions. Scope and Mechanistic Insights
  作者：Johan Franzén、Mauro Marigo、Doris Fielenbach、Tobias C. Wabnitz、Anne Kjærsgaard、Karl Anker Jørgensen

  DOI：10.1021/ja056120u

  日期：2005.12.1

  The development of a general organocatalyst for the alpha-functionalization of aldehydes, via an enamine intermediate, is presented. Based on optically active alpha,alpha-diarylprolinol silyl ethers, the scope and applications of this catalyst for the stereogenic formation of C-C, C-N, C-F, C-Br, and C-S bonds are outlined. The reactions all proceed in good to high yields and with excellent enantioselectivities. Furthermore, we will present mechanistic insight into the reaction course applying nonlinear effect studies, kinetic resolution, and computational investigations leading to an understanding of the properties of the alpha,alpha-diarylprolinol silyl ether catalysts.
• 3-Trifluoromethanesulfonamido-pyrrolidine:  A General Organocatalyst for <i>anti</i>-Selective Mannich Reactions
  作者：Mickael Pouliquen、Jérôme Blanchet、Marie-Claire Lasne、Jacques Rouden

  DOI：10.1021/ol8000975

  日期：2008.3.1

  Mannich-type reactions of a glyoxylate imine with carbonyl compounds catalyzed by 3-trifluoromethanesulfonamidopyrrolidine proceed with high yields and anti-stereoselectivity. The catalyst is easily prepared and the transformation appears to be quite general accommodating aldehydes or ketones.