(+/-)-cis-3,6-dibenzylpiperazine-2,5-dione | 2308-61-4

• 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: (+/-)-cis-3,6-dibenzylpiperazine-2,5-dione
• 英文别名: (3R,6R)-3,6-dibenzylpiperazine-2,5-dione
• CAS: 2308-61-4；2862-51-3；15136-18-2；16679-68-8；52438-42-3
• 化学式: C₁₈H₁₈N₂O₂
• 分子量: 294.353
• InChiKey: JUAPMRSLDANLAS-HZPDHXFCSA-N

物化性质

• 熔点：
  289-291 °C(Solv: ethanol (64-17-5))
• 沸点：
  594.2±43.0 °C(Predicted)
• 密度：
  1.186±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  58.2
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+/-)-cis-3,6-dibenzylpiperazine-2,5-dione 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 生成 (2R,5R)-2,5-dibenzylpiperazine
  参考文献：
  名称：

  Novel chiral N,N′-dimethyl-1,4-piperazines with metal binding abilities

  摘要：

  With the objective of developing novel chiral ligands, we report an efficient strategy to prepare chiral N,N-dimethyl-1,4-piperazines, six-member heterocyclic molecules that possess metal binding features. We prepared and characterized 18 piperazines, and evaluated their ability to complex different mono- and divalent metals, using a rapid picrate extraction technique. Some newly prepared diamine ligands were used in diethylzinc alkylation of aryl aldehydes. Yields increased significantly in the presence of the diamine ligands, though enantioselectivity was low. The results demonstrate the validity of the approach for preparing and identifying useful chiral diamine ligands. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.08.051
• 作为产物：
  描述：

  (R)-2-((r)-2-氨基-3-苯基丙酰胺)-3-苯基丙酸 生成 (+/-)-cis-3,6-dibenzylpiperazine-2,5-dione
  参考文献：
  名称：

  Vejdelek, Collection of Czechoslovak Chemical Communications, 1950, vol. 15, p. 929,931

  摘要：

  DOI：

文献信息

• Peptide bond formation by aminolysin-A catalysis: A simple approach to enzymatic synthesis of diverse short oligopeptides and biologically active puromycins
  作者：Hirokazu Usuki、Yukihiro Yamamoto、Jiro Arima、Masaki Iwabuchi、Shozo Miyoshi、Teruhiko Nitoda、Tadashi Hatanaka

  DOI：10.1039/c0ob00403k

  日期：——

  peptide bonds to give linear homo-oligopeptides, hetero-dipeptides, and cyclic dipeptides using cost-effective substrates in a one-pot reaction. Aminolysin-A can recognize several C-terminal-modified amino acids, including the L- and D-forms, as acyl donors as well as free amines, including amino acids and puromycin aminonucleoside, as acyl acceptors. The absence of amino acid esters prevents the formation

  新S9系列的氨肽酶从嗜热放线菌衍生Acidothermus了解纤维素被催化丝氨酸的定点突变克隆和工程化到transaminopeptidase 491到半胱氨酸。经过工程改造的生物催化剂，称为氨基溶素A，可以在一锅反应中使用经济高效的底物来催化肽键的形成，从而生成线性同型寡肽，杂二肽和环状二肽。氨基溶素A可以识别多个C末端修饰的氨基酸（包括L-和D-形式）作为酰基供体，以及游离胺（包括氨基酸和嘌呤霉素氨基核苷）作为酰基受体。氨基酸酯的缺乏阻止了肽的形成。因此，反应机理涉及氨解而不是水解的逆反应。氨基溶素系统将是通过简单方法制备结构多样的肽模拟物的有益工具。
• Pyrazine chemistry. II. Reduction of 3,6-Dibenzylidenepiperazine-2,5-diones
  作者：SM Marcuccio、JA Elix

  DOI：10.1071/ch9841791

  日期：——

  A reinvestigation of the reduction of 3,6-dibenzylidenepiperazine-2,5-dione (1) with zinc and acetic acid established that this reaction gave (Z)-6-benzyl-3-benzylidenepiperazine-2,5-dione (10). When a mixture of acetic acid and hydrochloric acid was used in the reduction, a mixture of trans- (12) and cis-3,6-dibenzylpiperazine-2,5-dione (5) was obtained. Direct catalytic reduction of 3,6-di(2-chloro- benzy1idene)piperazine-2,5-dione (2) to (�)-cis-3,6-di(2-chlorobenzyl)piperazine-2,5-dione (6) was also accomplished.

  对锌和乙酸还原 3,6-二苄基亚哌嗪-2,5-二酮 锌和乙酸还原 3,6-二苄基亚哌嗪-2,5-二酮 (1) 确定该反应生成了 (Z)-6-苄基-3-亚苄基哌嗪-2,5-二酮 (10)。当使用乙酸和盐酸的混合物 酸和盐酸的混合物进行还原时，可得到反式 (12) 和顺式-3,6-二苄基哌嗪-2,5-二酮 (5) 的混合物。直接 催化还原 3,6-二(2-氯亚苄基)哌嗪-2,5-二酮(2)至(......)。 (�)-顺式-3,6-二(2-氯苄基)哌嗪-2,5-二酮(6)。 (6)。
• USE OF RUTHENIUM COMPLEXES FOR FORMATION AND/OR HYDROGENATION OF AMIDES AND RELATED CARBOXYLIC ACID DERIVATIVES
  申请人：Milstein David

  公开号：US20120253042A1

  公开（公告）日：2012-10-04

  A process for preparing amides by reacting a primary amine and a primary alcohol in the presence of a Ruthenium complex to generate the amide and molecular hydrogen. Primary amines are directly acylated by equimolar amounts of alcohols to produce amides and molecular hydrogen (the only byproduct) in high yields and high turnover numbers. Also disclosed are processes for hydrogenation of amides to alcohols and amines; hydrogenation of organic carbonates to alcohols; hydrogenation of carbamates or urea derivatives to alcohols and amines; amidation of esters; acylation of alcohols using esters; coupling of alcohols with water and a base to form carboxylic acids; dehydrogenation of beta-amino alcohols to form pyrazines and cyclic dipeptides; and dehydrogenation of secondary alcohols to ketones. These reactions are catalyzed by a Ruthenium complex which is based on a dearomatized PNN-type ligand of formula A1 or precursors thereof of formulae A2 or A3.

  一种制备酰胺的方法，包括在Ruthenium配合物的存在下，通过反应一种一级胺和一种一级醇生成酰胺和分子氢。直接用等摩尔量的醇对一级胺进行酰化反应，可以高产率、高周转数地生成酰胺和分子氢（唯一的副产物）。此外，还揭示了将酰胺氢化为醇和胺的方法；将有机碳酸酯氢化为醇的方法；将氨基甲酸酯或尿素衍生物氢化为醇和胺的方法；酯的酰胺化反应；使用酯对醇进行酰化反应；将醇与水和碱偶联形成羧酸；将β-氨基醇脱氢生成吡嗪和环肽；以及将二级醇脱氢生成酮的方法。这些反应由基于A1式或A2式或A3式的去芳香的PNN型配体的Ruthenium配合物催化。
• NOVEL RUTHENIUM COMPLEXES AND THEIR USES IN PROCESSES FOR FORMATION AND/OR HYDROGENATION OF ESTERS, AMIDES AND DERIVATIVES THEREOF
  申请人：Milstein David

  公开号：US20130281664A1

  公开（公告）日：2013-10-24

  The present invention relates to novel Ruthenium catalysts and related borohydride complexes, and the use of such catalysts, inter alia, for (1) hydrogenation of amides (including polyamides) to alcohols and amines; (2) preparing amides from alcohols with amines (including the preparation of polyamides (e.g., polypeptides) by reacting dialcohols and diamines and/or by polymerization of amino alcohols); (3) hydrogenation of esters to alcohols (including hydrogenation of cyclic esters (lactones) or cyclic di-esters (di-lactones) or polyesters); (4) hydrogenation of organic carbonates (including polycarbonates) to alcohols and hydrogenation of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (5) dehydrogenative coupling of alcohols to esters; (6) hydrogenation of secondary alcohols to ketones; (7) amidation of esters (i.e., synthesis of amides from esters and amines); (8) acylation of alcohols using esters; (9) coupling of alcohols with water to form carboxylic acids; and (10) dehydrogenation of beta-amino alcohols to form pyrazines. The present invention further relates to the novel uses of certain pyridine Ruthenium catalysts.

  本发明涉及新型钌催化剂和相关硼氢化物配合物，以及使用这些催化剂，包括：（1）将酰胺（包括聚酰胺）加氢为醇和胺；（2）用胺从醇制备酰胺（包括通过二元醇和二胺反应或氨基醇聚合制备聚酰胺（例如聚肽））；（3）将酯加氢为醇（包括环酯（内酯）或环二酯（二内酯）或聚酯的加氢）；（4）将有机碳酸酯（包括聚碳酸酯）加氢为醇和将氨基甲酸酯（包括聚氨基甲酸酯）或脲衍生物加氢为醇和胺；（5）醇的脱氢缩合成酯；（6）将二级醇加氢为酮；（7）酯的酰胺化（即从酯和胺合成酰胺）；（8）使用酯对醇进行酰化；（9）将醇与水偶联形成羧酸；以及（10）β-氨基醇的脱氢缩合形成吡嗪的新用途。本发明还涉及某些吡啶基钌催化剂的新用途。
• Structure and synthesis of cis-3,6-dibenzyl-3,6-bis(methylthio)-piperazine-2,5-dione, a new metabolite of Aspergillus terreus
  作者：Gordon W. Kirby、David J. Robins、W. Marshall Stark

  DOI：10.1039/c39830000812

  日期：——

  The titled compound (1b), the first naturally occurring, sulphur-containing dioxopiperazine unsubstituted on nitrogen, has been isolated from Aspergillus terreus and synthesised via the corresponding epidisulphide (2d), which has been tested as a biosynthetic precursor of bisdethiobis(methylthio)acetylaranotin (3).

  已从土曲霉中分离出标题化合物（1b），这是第一种在氮上未被取代的天然存在的，含硫的二氧哌哌嗪，并通过相应的表二硫化物（2d）合成，该化合物已被测试为双脱硫双（甲硫基）乙酰基花生四烯酸的生物合成前体。 （3）。