N-γ-maleimidobutyric acid methyl ester | 423125-90-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: N-γ-maleimidobutyric acid methyl ester
• 英文别名: 4-maleimido-n-butanoic acid methyl ester；methyl 4-maleimidobutyrate；Methyl 4-(2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl)butanoate；methyl 4-(2,5-dioxopyrrol-1-yl)butanoate
• CAS: 423125-90-0
• 化学式: C₉H₁₁NO₄
• mdl: MFCD28168104
• 分子量: 197.191
• InChiKey: WFBGVOMBEJAXOG-UHFFFAOYSA-N

物化性质

• 熔点：
  56.5-57.5 °C
• 沸点：
  323.1±25.0 °C(Predicted)
• 密度：
  1.258±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.444
• 拓扑面积：
  63.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-γ-maleimidobutyric acid methyl ester 在 lithium hydroxide 、 三乙胺 作用下， 以 四氢呋喃 、 氯仿 、 氘代苯 、 水 为溶剂， 反应 48.0h， 生成 (2aR,7aS,7bR)-7b-Triisopropylsilanyloxy-hexahydro-furo[2,3,4-gh]pyrrolizine-2,6-dione
  参考文献：
  名称：

  价键异构体家族内的比较 Diels-Alder 反应性：(±)-UCS1025A 的仿生全合成

  摘要：

  完成了结构迷人的真菌代谢物 UCS1025A (1) 的合成。它的特点是通过推定的三烯前体 (2) 的分子内狄尔斯-阿尔德 (IMDA) 反应对八烷亚基进行仿生方法，然后在该化合物中有效构建二杂四喹烷亚基。具体而言，开发了分子内甲硅烷基三氟甲磺酸酯诱导的原位生成的甲硅烷基乙烯酮缩醛环化到酰亚胺羰基（例如，7至8）上。确定了价键异构体家族的 IMDA 相对反应性，每个异构体在亲二烯亚基的精确性质上都不同。在生物学相关条件下（D2O，pH 7.2 缓冲液，约 25 摄氏度），三烯 2 通过其内酯开环同源物，

  DOI：

  10.1021/ja0581999
• 作为产物：
  描述：

  甲醇 、 4-马来酰亚胺丁酸 在 氯化亚砜 作用下， 以78%的产率得到N-γ-maleimidobutyric acid methyl ester
  参考文献：
  名称：

  通过串联羰基化 Stille 交叉偶联和第尔斯-阿尔德反应全合成 UCS1025A†

  摘要：

  我们报告了一种高效且收敛的 UCS1025A 及其非对映异构体四表-UCS1025A全合成策略。UCS1025A是天然存在的吡咯齐啶酮聚酮化合物的代表性成员，已从中鉴定出具有有效抗菌、抗真菌和抗癌活性的成员。我们的方法采用串联羰基 Stille 交叉偶联和 Diels-Alder 反应来形成关键的 C—C 键并构建反式十氢化萘系统。该串联过程利用一氧化碳作为单碳关键，将乙烯基三氟甲磺酸酯和乙烯基锡烷缝合在一起，并形成随后的分子内狄尔斯-阿尔德环化所需的烯酮部分。我们的合成还为合成其他相关的含吡咯烷酮的聚酮化合物提供了一种通用的方法。

  DOI：

  10.1002/cjoc.202300331

文献信息

• Structure–reactivity relationships in a recognition mediated [3+2] dipolar cycloaddition reaction
  作者：Andrew J. Sinclair、Vicente del Amo、Douglas Philp

  DOI：10.1039/b908072d

  日期：——

  The [3+2] dipolar cycloaddition between an azide and maleimide can be accelerated by a factor of more than 100 simply by attaching complementary recognition sites to the reactive partners. This rate acceleration derives from the formation of a reactive binary complex between the azide and the maleimide. The variation of the observed rate acceleration with simple structural changes, such as adding additional rotors, should be relatively predictable. However, the application of a simple, rotor-based increment in the systems reported here is insufficient to predict reactivity correctly. Computational studies suggest that the nature of the available reaction pathways within the binary complex formed by the reactants is important in determining the reactivity of a given complex.

  通过在活性伙伴上附加互补识别位点，[3+2]偶极环加成反应中叠氮与马来酰亚胺之间的反应速度可以加快超过100倍。这种加速源于叠氮与马来酰亚胺之间反应性二元复合体的形成。观察到的反应加速对于简单的结构变化，如增加额外的旋转体，应该是相对可预测的。然而，对于此处报道的系统，仅依靠基于旋转体的简单增量不足以准确预测反应活性。计算研究表明，反应物形成的二元复合体内可用的反应路径的性质对于决定特定复合体的反应活性至关重要。
• Characterization of an RNA Active Site:  Interactions between a Diels−Alderase Ribozyme and Its Substrates and Products
  作者：Friedrich Stuhlmann、Andres Jäschke

  DOI：10.1021/ja0167405

  日期：2002.4.1

  substrates and accelerates cycloadditions with both enantio- and diastereoselectivity. The stereochemistry of the reaction is controlled by RNA-diene interactions. The RNA interacts strongly and stereoselectively with the cycloaddition products, requiring several structural features to be present. Taken together, the results highlight the intricacy of ribozyme active sites which can control chemical reaction

  最近已显示核酶催化小有机分子之间碳-碳键的立体选择性形成。这些 Diels-Alderase 核酶与其底物和产物的相互作用现已通过使用 44 种不同的、系统变化的类似物的化学取代分析得到阐明。RNA-二烯相互作用受堆叠相互作用控制，而氢键和金属离子配位似乎不太重要。二烯必须是蒽衍生物，并且允许在指定位置上有取代基，从而揭示结合位点的几何形状。亲二烯体必须是具有未取代反应性双键的五元马来酰亚胺环，疏水侧链对 RNA 结合有重要贡献。核酶区分手性底物的不同对映异构体，并以对映选择性和非对映选择性加速环加成。反应的立体化学由 RNA-二烯相互作用控制。RNA 与环加成产物强烈且立体选择性地相互作用，需要存在几个结构特征。总之，结果突出了核酶活性位点的复杂性，它可以根据底物立体化学和取代模式的微小差异控制化学反应途径。需要存在几个结构特征。总之，结果突出了核酶活性位点的复杂性，它可以根据底物立体化
• Skeletal Analogues of UCS1025A and B by Cyclization of Maleimides: Synthesis and Biological Activity
  作者：Mark G. Moloney、Lewis T. Ibbotson、Kirsten E. Christensen、Miroslav Genov、Alexander Pretsch、Dagmar Pretsch

  DOI：10.1055/s-0040-1719876

  日期：2022.3

  Application of a direct ring-closing approach which exploits an intramolecular aldol reaction with a ketene silyl acetal onto a remote imide function leading to the core skeleton of UCS1025A and B effectively provides access to small library of substituted analogues; of interest is their complete lack of antibacterial activity against MRSA (Gram+) and E. coli (Gram–) bacterial strains.

  摘要：应用一种直接环合成方法，利用内环醛缩反应和酮基硅醚在远离的亚胺基团上反应，形成UCS1025A和B的核心骨架，有效地提供了一系列取代类似物的访问途径；有趣的是它们完全缺乏对MRSA（革兰阳性）和大肠杆菌（革兰阴性）细菌菌株的抗菌活性。
• Process for producing polymerizable polybranched polyester
  申请人：Hayakawa Hitoshi

  公开号：US20060047140A1

  公开（公告）日：2006-03-02

  The present invention allows the production of a polymerizable hyperbranched polyester by introducing polymerizable unsaturated double bonds into the molecular terminals of a hyperbranched polyester polyol (A), which is obtained by condensation polymerization a polyhydroxy monocarboxylic acid in which there are at least two hydroxyl groups, the carbon atom adjacent to the carboxy group is saturated carbon atom, and the hydrogen atoms on said carbon atom are all substituted, by reacting the hyperbranched polyester polyol (A) and an alkyl ester of a carboxylic acid having a polymerizable unsaturated double bond (B) by a transesterification in the presence of at least one type of transesterification catalyst (C) selected from the group consisting of a dialkyl tin oxide and a stanoxane, without causing side reactions such as nucleophilic addition reactions of terminal hydroxyl groups to polymerizable unsaturated double bonds of the hyperbranched polyester polyol (A), or thermal polymerization of the polymerizable unsaturated double bonds. The polymerizable hyperbranched polyester can be produced at high efficiency using a transesterification that uses as an alkyl ester of a carboxylic acid having a polymerizable unsaturated double bond (B), which is easily obtained as an industrial raw material, and without altering the original backbone structure of the molecular chains of the hyperbranched polyester polyol (A) by hydrolysis and so forth.

  本发明通过在超支化聚酯多元醇（A）的分子端引入可聚合不饱和双键，从而允许生产可聚合的超支化聚酯。超支化聚酯多元醇（A）是通过缩聚至少含有两个羟基的聚羟基一元羧酸（羧基相邻的碳原子是饱和碳原子，该碳原子上的氢原子均被取代）而获得的。在至少一种转酯化催化剂（C）的存在下，通过将超支化聚酯多元醇（A）和具有可聚合不饱和双键的羧酸烷基酯（B）进行酯交换反应，而不引起末端羟基对超支化聚酯多元醇（A）的可聚合不饱和双键的亲核加成反应或热聚合反应等副反应，就可以高效地生产可聚合的超支化聚酯。使用作为工业原料易于获得的具有可聚合不饱和双键的羧酸烷基酯（B）进行酯交换反应，无需通过水解等改变超支化聚酯多元醇（A）的分子链的原始骨架结构。
• PROCESS FOR PRODUCING POLYMERIZABLE POLYBRANCHED POLYESTER
  申请人：DAINIPPON INK AND CHEMICALS, INC.

  公开号：EP1582548A1

  公开（公告）日：2005-10-05

  The present invention allows the production of a polymerizable hyperbranched polyester by introducing polymerizable unsaturated double bonds into the molecular terminals of a hyperbranched polyester polyol (A), which is obtained by condensation polymerization a polyhydroxy monocarboxylic acid in which there are at least two hydroxyl groups, the carbon atom adjacent to the carboxy group is saturated carbon atom, and the hydrogen atoms on said carbon atom are all substituted, by reacting the hyperbranched polyester polyol (A) and an alkyl ester of a carboxylic acid having a polymerizable unsaturated double bond (B) by a transesterification in the presence of at least one type of transesterification catalyst (C) selected from the group consisting of a dialkyl tin oxide and a stanoxane, without causing side reactions such as nucleophilic addition reactions of terminal hydroxyl groups to polymerizable unsaturated double bonds of the hyperbranched polyester polyol (A), or thermal polymerization of the polymerizable unsaturated double bonds. The polymerizable hyperbranched polyester can be produced at high efficiency using a transesterification that uses as an alkyl ester of a carboxylic acid having a polymerizable unsaturated double bond (B), which is easily obtained as an industrial raw material, and without altering the original backbone structure of the molecular chains of the hyperbranched polyester polyol (A) by hydrolysis and so forth.

  本发明通过在超支化聚酯多元醇（A）的分子末端引入可聚合的不饱和双键来生产可聚合的超支化聚酯，超支化聚酯多元醇（A）是通过缩合聚合多羟基一羧酸得到的，其中至少有两个羟基，与羧基相邻的碳原子是饱和碳原子，并且所述碳原子上的氢原子全部被取代、将超支化聚酯多元醇（A）和具有可聚合不饱和双键的羧酸烷基酯（B）在至少一种酯交换催化剂（C）（选自二烷基氧化锡和链烷氧基）的存在下进行酯交换反应、不引起副反应，如端羟基与超支化聚酯多元醇（A）的可聚合不饱和双键的亲核加成反应，或可聚合不饱和双键的热聚合反应。使用具有可聚合不饱和双键（B）的羧酸烷基酯进行酯交换反应，可高效生产可聚合超支化聚酯，该烷基酯可作为工业原料轻松获得，且不会通过水解等方式改变超支化聚酯多元醇（A）分子链的原始骨架结构。