1,4-bis((S)-1-phenylethyl)piperazine-2,5-dione | 158547-56-9

• 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: 1,4-bis((S)-1-phenylethyl)piperazine-2,5-dione
• 英文别名: 1,4-bis((S)-1-phenylethyl)piperazin-2,5-dione；1,4-N,N-[(S)-1-phenylethyl]-piperazine-2,5-dione；1,4-Bis[(s)-1-phenylethyl]piperazine-2,5-dione；1,4-bis[(1S)-1-phenylethyl]piperazine-2,5-dione
• CAS: 158547-56-9
• 化学式: C₂₀H₂₂N₂O₂
• 分子量: 322.407
• InChiKey: BODZAKWUNLOBLR-HOTGVXAUSA-N

物化性质

• 熔点：
  108-110 °C
• 沸点：
  547.0±50.0 °C(predicted)
• 密度：
  1.182±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  40.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,4-bis((S)-1-phenylethyl)piperazine-2,5-dione 在 lithium hexamethyldisilazane 作用下， 反应 10.0h， 生成 (3R,6S)-1,4-N,N-((S)-1-phenethyl)-3,6-(dibenzyl)piperazine-2,5-dione
  参考文献：
  名称：

  Synthesis of (3R,6R)- and (3S,6S)-3,6-dialkylpiperazin-2,5-dione derivatives as useful intermediates to both (R) and (S) α-aminoacids

  摘要：

  The alkylation of 2 leads to a diastereomeric mixture where 4 is generally present in greater amounts than 3. The successive alkylation of 4 affords exclusively the cis derivative 7, while a cis/trans mixture is obtained from isomer 3. In alkaline solution, the trans isomer 6 suffers a total conversion into a 1:1 mixture of the cis isomers 5 and 7 easily separated by silica gel chromatography. The configurations of the introduced stereogenic centers at C-3 and C-6 have been assigned on the basis of H-1-NMR spectroscopic data. Cleavage of heterocyclic ring of 5 and 7 leads to the corresponding (R)- and (S)-alpha-aminoacids respectively. Therefore, the substrate 2 appears a very useful chiral template to synthetize enantiomerically pure alpha-amino acids.

  DOI：

  10.1016/s0957-4166(00)86217-5
• 作为产物：
  描述：

  (4S)-N-((S)-1-phenyleth-1-yl)-4-phenyl-3-azapentanamide 在 正丁基锂 、 sodium carbonate 作用下， 以 四氢呋喃 、 正己烷 、 水 、 丙酮 为溶剂， 反应 14.0h， 生成 1,4-bis((S)-1-phenylethyl)piperazine-2,5-dione
  参考文献：
  名称：

  Synthesis of (3R,6R)- and (3S,6S)-3,6-dialkylpiperazin-2,5-dione derivatives as useful intermediates to both (R) and (S) α-aminoacids

  摘要：

  The alkylation of 2 leads to a diastereomeric mixture where 4 is generally present in greater amounts than 3. The successive alkylation of 4 affords exclusively the cis derivative 7, while a cis/trans mixture is obtained from isomer 3. In alkaline solution, the trans isomer 6 suffers a total conversion into a 1:1 mixture of the cis isomers 5 and 7 easily separated by silica gel chromatography. The configurations of the introduced stereogenic centers at C-3 and C-6 have been assigned on the basis of H-1-NMR spectroscopic data. Cleavage of heterocyclic ring of 5 and 7 leads to the corresponding (R)- and (S)-alpha-aminoacids respectively. Therefore, the substrate 2 appears a very useful chiral template to synthetize enantiomerically pure alpha-amino acids.

  DOI：

  10.1016/s0957-4166(00)86217-5

文献信息

• Selective, Catalytic, and Dual C(sp³)–H Oxidation of Piperazines and Morpholines under Transition-Metal-Free Conditions
  作者：Delfino Chamorro-Arenas、Urbano Osorio-Nieto、Leticia Quintero、Luís Hernández-García、Fernando Sartillo-Piscil

  DOI：10.1021/acs.joc.8b02564

  日期：2018.12.21

  innocuous reagents, such as NaClO2, NaOCl, and catalytic amounts of TEMPO, a new environmentally friendly protocol for the selective and catalytic TEMPO C(sp3)–H oxidation of piperazines and morpholines to 2,3-diketopiperazines (2,3-DKP) and 3-morpholinones (3-MPs), respectively, has been developed. This novel direct access to 2,3-DKP from piperazines provides significant advantages over the traditional

  通过使用廉价且无害的试剂（例如NaClO 2，NaOCl和催化量的TEMPO），将TEMPO C（sp 3）–H选择性和催化氧化哌嗪和吗啉氧化成2,3-二酮哌嗪的新环保协议（ 2,3-DKP）和3-吗啉酮（3-MP）已被开发出来。与传统的N-单酰化/分子内C–N环化方法相比，这种从哌嗪直接获得2,3-DKP的方法具有明显的优势。另外，通过调节TEMPO的量，可以从吗啉衍生物制备2-烷氧基氨基-3-吗啉酮，这将使吗啉骨架的C2位进一步官能化。
• Synthesis of Bridged Diketopiperazines by Using the Persistent Radical Effect and a Formal Synthesis of Bicyclomycin
  作者：Tynchtyk Amatov、Radek Pohl、Ivana Císařová、Ullrich Jahn

  DOI：10.1002/anie.201504883

  日期：2015.10.5

  A conceptually new and unified approach to diverse bridged diketopiperazines (DKPs) with widely variable ring sizes was developed by taking advantage of the persistent radical effect. This method enables synthesis of the core structures of bridged DKP alkaloids and was applied to a formal synthesis of the antibiotic bicyclomycin.

  利用持久的激进效应，开发了一种概念新颖的统一方法，用于处理各种环大小可变的桥联二酮哌嗪（DKP）。该方法能够合成桥接的DKP生物碱的核心结构，并被用于抗生素双环霉素的正式合成。
• A chiral relay auxiliary for the synthesis of homochiral α-amino acids
  作者：Steven D. Bull、Stephen G. Davies、Simon W. Epstein、Michael A. Leech、Jacqueline V. A. Ouzman

  DOI：10.1039/a803124j

  日期：——

  A new chiral auxiliary (3S)-N,N′-bis(p-methoxybenzyl)-3-isopropylpiperazine-2,5-dione 7 has been developed for the asymmetric synthesis of α-amino acids. The auxiliary 7 employs a novel chiral relay network based on non-stereogenic N-benzyl protecting groups which enhance the diastereoselectivity observed during alkylation of its C6 enolate 25.

  我们开发了一种新的手性辅助剂 (3S)-N,Nâ²-双（对甲氧基苄基）-3-异丙基哌嗪-2,5-二酮 7，用于δ-氨基酸的不对称合成。辅助剂 7 采用了一种基于非固有 N-苄基保护基团的新型手性中继网络，从而提高了其 C6 对映体 25 烷基化过程中观察到的非对映选择性。
• From amines to diketopiperazines: a one-pot approach
  作者：Elaine O’Reilly、Lara Pes、Francesca Paradisi

  DOI：10.1016/j.tetlet.2010.01.075

  日期：2010.3

  An efficient one-pot synthesis is described for the preparation of 1,4-disubstituted piperazine-2,5-diones starting from a suitable amine and chloroacetyl chloride in the presence of an aqueous base. The resulting chloroacetamide is cyclised in situ by employing the phase-transfer (PT) catalyst, benzyltriethylammonium chloride (TEBA). The products are isolated in excellent yields of up to 90%.

  描述了一种有效的一锅合成，该合成用于在水性碱的存在下从合适的胺和氯乙酰氯开始制备1，4-二取代的哌嗪-2，5-二酮。通过使用相转移（PT）催化剂苄基三乙基氯化铵（TEBA）将所得的氯乙酰胺原位环化。分离出的产物产率高达90％。
• One-step diketopiperazine synthesis using phase transfer catalysis
  作者：Elaine O’Reilly、Elena Lestini、Daniele Balducci、Francesca Paradisi

  DOI：10.1016/j.tetlet.2009.01.146

  日期：2009.4

  A simple and efficient one-step procedure is described for the synthesis of a number of symmetrical 1,4-disubstituted piperazine-2,5-diones under phase transfer conditions. The reactions are carried out at room temperature, starting from a suitable N-chloroacetamide in the presence of an aqueous solution of sodium hydroxide. Piperazine-2,5-diones were obtained with excellent selectivity in yields of

  描述了一种简单有效的一步程序，用于在相转移条件下合成许多对称的1,4-二取代哌嗪-2,5-二酮。反应在室温下进行，从合适的N-氯乙酰胺开始，在氢氧化钠水溶液的存在下进行。获得具有高达90％的产率的优异选择性的哌嗪-2，5-二酮。