(3S,6R)-N,N'-bis-(p-methoxybenzyl)-3-isopropyl-6-benzyl-piperazine-2,5-dione | 205517-36-8

• 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: (3S,6R)-N,N'-bis-(p-methoxybenzyl)-3-isopropyl-6-benzyl-piperazine-2,5-dione
• 英文别名: (3R,6S)-N,N'-bis-(4-methoxybenzyl)-3-benzyl-6-isopropyl-piperazine-2,5-dione；(3R,6S)-3-benzyl-1,4-bis[(4-methoxyphenyl)methyl]-6-propan-2-ylpiperazine-2,5-dione
• CAS: 205517-36-8
• 化学式: C₃₀H₃₄N₂O₄
• 分子量: 486.611
• InChiKey: LKFIDMHTNDHBKC-IZLXSDGUSA-N

物化性质

• 沸点：
  693.4±55.0 °C(Predicted)
• 密度：
  1.168±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  36
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  59.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (3S,6R)-N,N'-bis-(p-methoxybenzyl)-3-isopropyl-6-benzyl-piperazine-2,5-dione 在 正丁基锂 、 ammonium cerium(IV) nitrate 、 2,6-二叔丁基苯酚 作用下， 以 乙腈 为溶剂， 生成 cyclo(L-Phe-L-Val)
  参考文献：
  名称：

  Deracemisation of α-amino acids—(R)- and (S)-phenylalanine from the same enantiomer of a homochiral auxiliary

  摘要：

  Chiral auxiliary (3S)-N,N'-bis-(p-methoxybenzyl)-3-isopropylpiperazine-2,5-dione 1 was employed for the synthesis of both enantiomers of phenylalanine using a regioselective deprotonation/stereoselective reprotonation strategy. Modification of th is approach enables the efficient deracemisation of (+/-)-phenylalanine. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(98)00304-8
• 作为产物：
  描述：

  (S)-3-异丙基-2,5-哌嗪二酮 在 sodium hydride 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 生成 (3S,6R)-N,N'-bis-(p-methoxybenzyl)-3-isopropyl-6-benzyl-piperazine-2,5-dione
  参考文献：
  名称：

  Chiral relay auxiliary for the synthesis of enantiomerically pure α-amino acids

  摘要：

  手性辅助剂（3S）-N,N′-双（对甲氧基苄基）-3-异丙基哌嗪-2,5-二酮利用基于非立体中心的N-苄基保护基团的手性中继网络，以增强酮酸酯烷基化过程中的非对映选择性控制。

  DOI：

  10.1039/a800407b

文献信息

• Asymmetric conjugate reductions with samarium diiodide: asymmetric synthesis of (2S,3R)- and (2S,3S)-[2-²H,3-²H]-leucine-(S)-phenylalanine dipeptides and (2S,3R)-[2-²H,3-²H]-phenylalanine methyl ester
  作者：Stephen G. Davies、Humberto Rodríguez-Solla、Juan A. Tamayo、Andrew R. Cowley、Carmen Concellón、A. Christopher Garner、Alastair L. Parkes、Andrew D. Smith

  DOI：10.1039/b500566c

  日期：——

  diastereoselective samarium diiodide and D(2)O-promoted conjugate reduction of homochiral (E)- and (Z)-benzylidene and isobutylidene diketopiperazines (E)-5,7 and (Z)-6,8 has been demonstrated. This methodology allows the asymmetric synthesis of methyl (2S,3R)-dideuteriophenylalanine 27 in > or = 95% de and >98% ee, and (2S,3R)- or (2S,3S)-dideuterioleucine-(S)-phenylalanine dipeptides 37 and 38 in moderate de,

  已经证明了高度非对映选择性的二碘化and和D（2）O促进的同手性（E）-和（Z）-亚苄基和异丁烯二酮哌嗪（E）-5,7和（Z）-6,8的共轭还原。这种方法学允许不对称合成95％de和98％ee或以下的（2S，3R）-或（2S，3S）-二氘代亮氨酸-（S）-苯丙氨酸的甲基（2S，3R）-二氘代苯丙氨酸二肽37和38分别处于中等水平，分别为66％和74％。提出了一种机制来说明此过程。
• Diastereoselective synthesis of quaternary α-amino acids from diketopiperazine templates
  作者：Stephen G. Davies、A. Christopher Garner、Jaqueline V. A. Ouzman、Paul M. Roberts、Andrew D. Smith、Emma J. Snow、James E. Thomson、Juan A. Tamayo、Richard J. Vickers

  DOI：10.1039/b704475e

  日期：——

  Sequential enolate alkylations of (S)-N(1)-methyl-5-methoxy-6-isopropyl-3,6-dihydropyrazin-2-one and (S)-N(1)-p-methoxybenzyl-5-methoxy-6-isopropyl-3,6-dihydropyrazin-2-one proceed with excellent levels of diastereoselectivity (>90% de) affording quaternary α-amino acids in high enantiomeric excess (>98% ee) after deprotection and hydrolysis.

  (S)-N(1)-甲基-5-甲氧基-6-异丙基-3,6-二氢吡嗪-2-酮和(S)-N(1)-对甲氧基苄基-5-甲氧基-6-异丙基-3,6-二氢吡嗪-2-酮的顺序对映体烷基化反应以极好的非对映选择性（>90% de）进行，以高对映体过量（>90% de）得到季δ-氨基酸、6- 二氢嗪-2-酮的非对映选择性极佳（de>90%），在脱保护和水解后可得到对映体过量（ee>98%）的季δ-氨基酸。
• 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。
• 2-Halo-diketopiperazines as chiral glycine cation equivalents
  作者：Steven D. Bull、Stephen G. Davies、A. Christopher Garner、Edward D. Savory、Emma J. Snow、Andrew D. Smith

  DOI：10.1016/j.tetasy.2004.11.022

  日期：2004.12

  A range of (2S,5S)-5-isopropyl-2-halo-N,N-1-bis-(p-methoxybenzyl)-piperazine-3,6-diones 8 (Cl),11,12 (F) and 13 (Br) have been prepared, either via electrophilic halogenation of the corresponding lithiated diketopiperazine, or via transhalogenation from fluoro-11 and 12. The product distribution and stereo selectivity of additions of allyltrimethylsilane, sodium thiophenolate and a range of organomagnesium reagents to chloro 8 are reported. In the reactions with Grignard reagents the observed stereo- and regioselectivities are dependent on the reagent employed, with C-3 carbonyl addition products predominating upon addition of allyl or methlmagnesium chloride and stereodivergent formal C-2 addition predominating with benzyl or isopropylmagnesium chloride. A model to account for the different reactivity and stereo selectivity in these reactions is proposed. (C) 2004 Published by Elsevier Ltd.
• Deracemisation of α-amino acids—(R)- and (S)-phenylalanine from the same enantiomer of a homochiral auxiliary
  作者：Steven D Bull、Stephen G Davies、Simon W Epstein、Jacqueline V.A Ouzman

  DOI：10.1016/s0957-4166(98)00304-8

  日期：1998.8

  Chiral auxiliary (3S)-N,N'-bis-(p-methoxybenzyl)-3-isopropylpiperazine-2,5-dione 1 was employed for the synthesis of both enantiomers of phenylalanine using a regioselective deprotonation/stereoselective reprotonation strategy. Modification of th is approach enables the efficient deracemisation of (+/-)-phenylalanine. (C) 1998 Elsevier Science Ltd. All rights reserved.