tert-butyl 5-oxo-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: tert-butyl 5-oxo-3-phenylpyrrolidine-2-carboxylate
• 英文别名: tert-butyl (2S,3R)-5-oxo-3-phenylpyrrolidine-2-carboxylate
• 化学式: C₁₅H₁₉NO₃
• 分子量: 261.321
• InChiKey: CSVJUEUGWAPWJI-YPMHNXCESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  55.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  1-tert-butyl methyl (2R*,3R*)-2-<(1R,4R)-bornylideneamino>-3-phenylglutarate 在 羟胺 、 溶剂黄146 作用下， 以 乙醇 为溶剂， 反应 2.0h， 以82%的产率得到tert-butyl 5-oxo-3-phenylpyrrolidine-2-carboxylate
  参考文献：
  名称：

  Highly diastereoselective Michael addition of lithiated camphor imines of glycine esters to .alpha.,.beta.-unsaturated esters. Synthesis of optically pure 5-oxo-2,4-pyrrolidinedicarboxylates of unnatural stereochemistry

  摘要：

  The lithium enolates of camphor imines of glycine esters underwent highly diastereoselective Michael additions to alpha,beta-unsaturated esters. The tightly chelated structure of the Z,E enolates and the selective approach of the alpha,beta-unsaturated esters to the re face of the enolates were responsible for the high diastereoselectivity observed. The use of alkylidenemalonate acceptors led to the diastereospecific formation of Michael adducts. Removal of the camphor auxiliary of the adducts and concomitant cyclization led to optically pure enantiomeric 5-oxo-2,4-pyrrolidinedicarboxylates of unnatural stereochemistry.

  DOI：

  10.1021/jo00008a052

文献信息

• Enantioselective Synthesis of Pyroglutamic Acid Esters from Glycinate via Carbonyl Catalysis
  作者：Jiguo Ma、Qinghai Zhou、Guanshui Song、Yongchang Song、Guoqing Zhao、Kuiling Ding、Baoguo Zhao

  DOI：10.1002/anie.202017306

  日期：2021.5.3

  Direct α‐functionalization of NH2‐free glycinates with relatively weak electrophiles such as α,β‐unsaturated esters still remains a big challenge in organic synthesis. With chiral pyridoxal 5 d as a carbonyl catalyst, direct asymmetric conjugated addition at the α‐C of glycinate 1 a with α,β‐unsaturated esters 2 has been successfully realized, to produce various chiral pyroglutamic acid esters 4 in 14–96 %

  用相对较弱的亲电试剂（例如，α，β-不饱和酯）将不含NH 2的甘氨酸直接进行α-官能化仍然是有机合成中的一大挑战。以手性吡ido醛5 d作为羰基催化剂，已成功实现在甘氨酸1a的α-C与α，β-不饱和酯2的直接不对称共轭加成反应，以14-96％的收率生产各种手性焦谷氨酸酯4原位内酰胺化后具有81–97％ee的物质。该反式与顺非对映异构体可以通过色谱法同时获得，并且可以很容易地通过叔丁基去除和随后的Barton转化为手性4取代的吡咯烷-2-酮，例如具有相同绝对构型的阿兹海默氏药物Rolipram（11）。脱羧。
• Multicomponent synthesis of pyroglutamic acid derivatives <i>via</i> Knoevenagel–Michael-hydrolysis-lactamization-decarboxylation (KMHL-D) sequence
  作者：Tushar M. Khopade、Prakash K. Warghude、Amol D. Sonawane、Ramakrishna G. Bhat

  DOI：10.1039/c8ob02473a

  日期：——

  and practical method for the synthesis of 3-substituted pyroglutamic acid derivatives is described. One pot multicomponent reaction of Meldrum's acid, aldehyde and Schiff's base followed an unprecedented chemoselective Knoevenagel–Michael-hydrolysis-lactamization domino sequence to afford 4-carboxy 3-substituted pyroglutamic acid derivatives under mild conditions. A carboxy intermediate formed appears

  描述了一种合成3-取代的焦谷氨酸衍生物的新颖实用的方法。Meldrum的酸，醛和Schiff碱的一锅多组分反应遵循空前的化学选择性Knoevenagel-Michael-水解-内酰胺化多米诺序列，可在温和条件下提供4-羧基3-取代的焦谷氨酸衍生物。形成的羧基中间体似乎加速了其自身的形成。合成的普遍性通过使用包括可烯醇化的脂族醛在内的多种醛来举例说明，而底物在反应条件下是稳定的。
• Stereodivergent silver-catalyzed synthesis of pyroglutamic acid esters
  作者：Byungjun Kim、Yuna Song、Sarah Yunmi Lee

  DOI：10.1039/d1cc04875a

  日期：——

  We report here a silver-catalyzed method for the enantio- and diastereodivergent synthesis of chiral pyroglutamic acid esters with multiple stereocenters. This process proceeds through asymmetric conjugate addition of glycine imine esters to a broad range of β-substituted α,β-unsaturated perfluorophenyl esters followed by lactamization. By leveraging catalyst control and stereospecificity of the 1

  我们在这里报告了一种银催化的方法，用于具有多个立体中心的手性焦谷氨酸酯的对映和非对映发散合成。该过程通过将甘氨酸亚胺酯不对称共轭加成到范围广泛的 β-取代的 α,β-不饱和全氟苯基酯，然后进行内酰胺化来进行。通过利用 1,4-加成过程的催化剂控制和立体定向性，可以以高立体选择性获得所有包含两个相邻立体中心的四种产物立体异构体。
• Diastereoselective Synthesis of Substituted Glutamic Acid Derivatives via Michael Additions of N-[Bis(methylthio)methylene]glycinates under Solid-Liquid Phase Transfer Catalysis
  作者：Carlos Alvarez-Ibarra、Aurelio G. Csakye、Mercedes Maroto、M. Luz Quiroga

  DOI：10.1021/jo00126a020

  日期：1995.10

  Michael additions of the enolates of ethyl and tert-butyl N-[bis(methylthio)methylene]glycinates with alpha,beta-unsaturated esters and ketones under solid-liquid phase transfer catalysis allowed for the highly diastereoselective synthesis of substituted glutamic acid derivatives through a transition state chelation-controlled by the catalyst with a like approach of reactants. Selective removal of the iminodithiocarbonate protecting group with concomitant cyclization gave rise to 3-substituted pyroglutamates and 1,3,4-trisubstitued Delta(1)-pyrrolines with retention of configuration.
• Highly diastereoselective Michael addition of lithiated camphor imines of glycine esters to .alpha.,.beta.-unsaturated esters. Synthesis of optically pure 5-oxo-2,4-pyrrolidinedicarboxylates of unnatural stereochemistry
  作者：Shuji Kanemasa、Akira Tatsukawa、Eiji Wada

  DOI：10.1021/jo00008a052

  日期：1991.4

  The lithium enolates of camphor imines of glycine esters underwent highly diastereoselective Michael additions to alpha,beta-unsaturated esters. The tightly chelated structure of the Z,E enolates and the selective approach of the alpha,beta-unsaturated esters to the re face of the enolates were responsible for the high diastereoselectivity observed. The use of alkylidenemalonate acceptors led to the diastereospecific formation of Michael adducts. Removal of the camphor auxiliary of the adducts and concomitant cyclization led to optically pure enantiomeric 5-oxo-2,4-pyrrolidinedicarboxylates of unnatural stereochemistry.