ethyl (2S,4R)-1-(tert-butoxycarbonyl)-4-benzylpyroglutamate | 153080-85-4

• 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: ethyl (2S,4R)-1-(tert-butoxycarbonyl)-4-benzylpyroglutamate
• 英文别名: Ethyl (4R)-4-benzyl-N-Boc-pyroglutamate；1-O-tert-butyl 2-O-ethyl (2S,4R)-4-benzyl-5-oxopyrrolidine-1,2-dicarboxylate
• CAS: 153080-85-4
• 化学式: C₁₉H₂₅NO₅
• 分子量: 347.411
• InChiKey: LDUBNPSIHNXHQF-CABCVRRESA-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：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  72.9
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl (2S,4R)-1-(tert-butoxycarbonyl)-4-benzylpyroglutamate 在 三乙基硼氢化锂 、 对甲苯磺酸 作用下， 以 四氢呋喃 为溶剂， 反应 1.08h， 生成 (4R)-N^α-tert-butoxycarbonyl-4-benzyl-5-methoxy-L-proline ethyl ester
  参考文献：
  名称：

  立体选择性合成二肽β-turn模拟物：7-苄基和8-苯基取代的氮杂双环[4.3.0]壬烷氨基酸酯。

  摘要：

  已开发出一种立体选择性方法，用于合成7和8位取代的二肽β-turn模拟氮杂双环[4.3.0]壬烷氨基酸酯。烯丙基以高非对映体选择性引入，分别由焦谷氨酸衍生物3或9中的3-苯基或4-苄基控制。用Burk的DuPHOS Rh（I）基催化剂对前体衍生自5或11的脱氢氨基酸7和13进行不对称氢化，以高立体选择性提供α-氨基酸衍生物。所得氨基酸8和14以高收率转化成β-转类似物6，5-双环内酰胺1a-d。

  DOI：

  10.1021/jo0203591
• 作为产物：
  描述：

  BOC-L-焦谷氨酸乙酯 、 alkaline earth salt of/the/ methylsulfuric acid 在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 生成 ethyl (2S,4R)-1-(tert-butoxycarbonyl)-4-benzylpyroglutamate
  参考文献：
  名称：

  Design and Synthesis of Potent, Non-peptide Inhibitors of HCV NS3 Protease

  摘要：

  Starting from a hexapeptide boronic acid lead, 3-amino bicyclic pyrazinones as novel beta-sheet dipeptide mimetics have been designed and synthesized. Side-chain manipulation of this scaffold generated a series of potent, nonpeptidic inhibitors of HCV NS3 protease. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0960-894x(03)00032-5

文献信息

• New enantioselective approach to α-allokainoids by Michael addition to chiral 4-substituted 2,3-didehydroprolinate
  作者：Jesús Ezquerra、Ana Escribano、Almudena Rubio、Modesto Jesús Remuiñán、Juan JoséVaquero

  DOI：10.1016/0040-4039(95)01165-e

  日期：1995.8

  (-) and (+) alpha-Allokainoids hydrochlorides 3 and 4 were obtained by hydrolysis of the corresponding Michael adducts resulting from the addition of diethyl malonate to chiral N-urethane protected ethyl 4-benzyl-2,3-didehydroprolinates 9 and 13 respectively.

  (-)和(+) α-取代的水合氯醛盐酸盐3和4分别通过水解相应的迈克尔加成物而得到，这些加成物来源于二乙酸精氨酸酯分别加成到手性N-脲保护的乙基4-苄基-2,3-去氢脯氨酸酯9和13上。
• Stereoselective reactions of lithium enolates derived from N-BOC protected pyroglutamic esters
  作者：Jesús Ezquerra、Concepción Pedregal、Almudena Rubio、Belén Yruretagoyena、Ana Escribano、Francisco Sánchez-Ferrando

  DOI：10.1016/s0040-4020(01)96272-6

  日期：1993.9

  The lithium enolates of N-Boc protected pyroglutamic ethyl or tert-butyl esters react with electrophiles in good yield without epimerization of the chiral centre. With benzyl bromides the process is stereospecific, yielding exclusively the trans isomer. However, with other reactive electrophiles a 2:1 trans/cis diastereomeric mixture was obtained, regardless of the steric bulk of the ester group.

  N-Boc保护的焦谷氨酸乙酯或叔丁酯的烯醇锂与亲电子试剂的收率很好，而没有手性中心的差向异构化。对于苄基溴，该过程是立体有向的，仅产生反式异构体。但是，与其他反应性亲电试剂相比，无论酯基团的空间体积如何，均获得了2：1的反式/顺式非对映异构体混合物。
• Stereoselective Double Alkylation of Ethyl N-Boc-pyroglutamate
  作者：Jesus Ezquerra、Concepcion Pedregal、Almudena Rubio、Juan Jose Vaquero、Maria Paz Matia、Justina Martin、Adolfo Diaz、J. L. G. Navio、Jack B. Deeter

  DOI：10.1021/jo00094a057

  日期：1994.7
• Stereoselective Addition of Grignard-Derived Organocopper Reagents to N-Acyliminium Ions: Synthesis of Enantiopure 5- and 4,5-Substituted Prolinates
  作者：Ivan Collado、Jesus Ezquerra、Concepcion Pedregal

  DOI：10.1021/jo00121a020

  日期：1995.8

  Alkylation of nonracemic N-acyliminium ions derived from proline and 4-substituted prolines has been extended to different types of Grignard-derived organocopper reagents. The reaction proceeds with high yield and stereoselectivity to yield 5-mono- and 4,5-disubstituted prolinates. The stereochemistry is controlled by the formation of a RCu-pi complex intermediate between the N-acyliminium ion, the carbonyl group of the ester, and the copper species.
• Design and Synthesis of Potent, Non-peptide Inhibitors of HCV NS3 Protease
  作者：Xiaojun Zhang、Aaron C. Schmitt、Wen Jiang、Zelda Wasserman、Carl P. Decicco

  DOI：10.1016/s0960-894x(03)00032-5

  日期：2003.3

  Starting from a hexapeptide boronic acid lead, 3-amino bicyclic pyrazinones as novel beta-sheet dipeptide mimetics have been designed and synthesized. Side-chain manipulation of this scaffold generated a series of potent, nonpeptidic inhibitors of HCV NS3 protease. (C) 2003 Elsevier Science Ltd. All rights reserved.