(R)-2-benzylsuccinate

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 苯丙酸
• 英文名称: (R)-2-benzylsuccinate
• 英文别名: (2R)-2-benzylbutanedioate
• 化学式: C11H10O4-2
• 分子量: 206.19
• InChiKey: GTOFKXZQQDSVFH-SECBINFHSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  80.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-2-benzylsuccinate 、 succinyl-CoA(5-) 生成 (R)-2-benzylsuccinyl-CoA 、 琥珀酸根
  参考文献：
  名称：

  Anaerobic toluene-catabolic pathway in denitrifying Thauera aromatica: activation and β-oxidation of the first intermediate, (R)-(+)-benzylsuccinate

  摘要：

  甲苯的厌氧分解代谢是通过将甲苯的甲基加到富马酸共底物的双键上生成第一个中间产物--苄基琥珀酸酯而开始的。正如反硝化细菌 Thauera aromatica 所示，这一反应是由糖基自由基酶苄基琥珀酸合酶催化的。苄基琥珀酸进一步氧化成苯甲酰-CoA，这是芳香族化合物厌氧降解的核心中间产物。作者通过对甲苯生长的芳香菌细胞提取物的实验表明，苄基丁二酸氧化的途径需要在甲苯诱导的、依赖琥珀酰-CoA的可逆性 CoA-转移酶催化下，将游离酸活化为 CoA-硫酯。在甲苯生长细胞的提取物中，CoA-转移酶反应的产物--苄基琥珀酰-CoA 被氧化为苯甲酰-CoA 和琥珀酰-CoA，从而为所提出的厌氧甲苯代谢途径提供了证据。分析了催化苄基丁二酸酯形成和活化的酶的立体化学偏好。发现苄基琥珀酸合成酶只产生(R)-(+)-苄基琥珀酸，尽管该酶的拟议反应机制是通过自由基中间体进行的。与此相对应，琥珀酰-CoA：苄基琥珀酸 CoA 转移酶的反应也专门针对(R)-(+)-苄基琥珀酸，而不与(S)-(-)-对映体发生反应。

  DOI：

  10.1099/00221287-145-11-3265

文献信息

• Anaerobic toluene-catabolic pathway in denitrifying Thauera aromatica: activation and β-oxidation of the first intermediate, (R)-(+)-benzylsuccinate
  作者：Christina Leutwein、Johann Heider

  DOI：10.1099/00221287-145-11-3265

  日期：1999.11.1

  Anaerobic catabolism of toluene is initiated by addition of the methyl group of toluene to the double bond of a fumarate cosubstrate to yield the first intermediate, benzylsuccinate. This reaction is catalysed by the glycyl-radical enzyme benzylsuccinate synthase, as shown for the denitrifying bacterium Thauera aromatica. Benzylsuccinate is further oxidized to benzoyl-CoA, the central intermediate of anaerobic degradation of aromatic compounds. The authors show here by experiments with cell extracts of toluene-grown T. aromatica that the pathway of benzylsuccinate oxidation requires activation of the free acid to a CoA-thioester, catalysed by a toluene-induced, reversible succinyl-CoA-dependent CoA-transferase. The product of the CoA-transferase reaction, benzylsuccinyl-CoA, is oxidized to benzoyl-CoA and succinyl-CoA in extracts of toluene-grown cells, adding proof to the proposed anaerobic toluene-catabolic pathway. The stereochemical preferences of the enzymes catalysing formation and activation of benzylsuccinate have been analysed. Benzylsuccinate synthase was found to produce exclusively (R)-(+)-benzylsuccinate, although the proposed reaction mechanism of this enzyme proceeds via radical intermediates. In accordance, the reaction of succinyl-CoA:benzylsuccinate CoA-transferase is also specific for (R)-(+)-benzylsuccinate and does not proceed with the (S)-(−)-enantiomer.

  甲苯的厌氧分解代谢是通过将甲苯的甲基加到富马酸共底物的双键上生成第一个中间产物--苄基琥珀酸酯而开始的。正如反硝化细菌 Thauera aromatica 所示，这一反应是由糖基自由基酶苄基琥珀酸合酶催化的。苄基琥珀酸进一步氧化成苯甲酰-CoA，这是芳香族化合物厌氧降解的核心中间产物。作者通过对甲苯生长的芳香菌细胞提取物的实验表明，苄基丁二酸氧化的途径需要在甲苯诱导的、依赖琥珀酰-CoA的可逆性 CoA-转移酶催化下，将游离酸活化为 CoA-硫酯。在甲苯生长细胞的提取物中，CoA-转移酶反应的产物--苄基琥珀酰-CoA 被氧化为苯甲酰-CoA 和琥珀酰-CoA，从而为所提出的厌氧甲苯代谢途径提供了证据。分析了催化苄基丁二酸酯形成和活化的酶的立体化学偏好。发现苄基琥珀酸合成酶只产生(R)-(+)-苄基琥珀酸，尽管该酶的拟议反应机制是通过自由基中间体进行的。与此相对应，琥珀酰-CoA：苄基琥珀酸 CoA 转移酶的反应也专门针对(R)-(+)-苄基琥珀酸，而不与(S)-(-)-对映体发生反应。
• Anaerobic Toluene Catabolism of <i>Thauera aromatica</i> : the <i>bbs</i> Operon Codes for Enzymes of β Oxidation of the Intermediate Benzylsuccinate
  作者：Birgitta Leuthner、Johann Heider

  DOI：10.1128/jb.182.2.272-277.2000

  日期：2000.1.15

  The pathway of anaerobic toluene oxidation to benzoyl coenzyme A (benzoyl-CoA) consists of an initial reaction catalyzed by benzylsuccinate synthase, a glycyl radical enzyme adding the methyl group of toluene to the double bond of a fumarate cosubstrate, and a subsequent β-oxidation pathway of benzylsuccinate. Benzylsuccinate synthase has been studied in some detail, whereas the enzymes participating in β oxidation of benzylsuccinate are unknown. We have investigated these enzymes by analyzing substrate-induced proteins in toluene-grown cells. Toluene-induced proteins were identified and N-terminally sequenced. Nine of these proteins are encoded by an 8.5-kb operon consisting of bbs (beta-oxidation of benzylsuccinate) genes whose products are apparently involved in the β-oxidation pathway of benzylsuccinate. Two of the genes, bbsE and bbsF , code for the subunits of a succinyl-CoA:benzylsuccinate CoA-transferase whose activity was previously detected in toluene-grown Thauera aromatica . The bbsG gene codes for a specific benzylsuccinyl-CoA dehydrogenase, as confirmed by overexpression of the gene in Escherichia coli and detection of enzyme activity. The further enzymes of the pathway are probably encoded by bbsH (enoyl-CoA hydratase), bbsCD (3-hydroxyacyl-CoA dehydrogenase), and bbsB (3-oxoacyl-CoA thiolase). The operon contains two additional genes, bbsA and bbsI , for which no obvious function could be derived. The bbs operon is expressed only in toluene-grown cells and is regulated at the transcriptional level. Promoter mapping revealed a transcription start site upstream of the bbsA gene. This represents the first known promoter site in Thauera spp.

  摘要 厌氧甲苯氧化成苯甲酰辅酶 A（苯甲酰-CoA）的途径包括由苄基琥珀酸合成酶催化的初始反应（一种将甲苯的甲基加到富马酸共底物双键上的糖基自由基酶）和随后的苄基琥珀酸β氧化途径。对苄基琥珀酸合成酶进行了较为详细的研究，但参与苄基琥珀酸β氧化的酶还不清楚。我们通过分析甲苯生长细胞中底物诱导蛋白来研究这些酶。我们鉴定了甲苯诱导的蛋白质，并对其进行了 N 端测序。其中九种蛋白由一个 8.5 kb 的操作子编码，该操作子包括 bbs (苄基琥珀酸的β-氧化)基因所编码，这些基因的产物显然参与了苄基琥珀酸的β-氧化途径。其中两个基因 bbsE 和 bbsF 编码琥珀酰-CoA：苄基琥珀酸 CoA 转移酶的亚基。 Thauera aromatica .该 bbsG 基因编码一种特定的苄基琥珀酰-CoA 脱氢酶。 大肠杆菌 并检测酶的活性。该途径的其他酶可能由 bbsH (烯酰-CoA水解酶）编码、 bbsCD (3-hydroxyacyl-CoA dehydrogenase）和 bbsB (3-oxoacyl-CoA 硫醇酶）。该操作子包含另外两个基因、 bbsA 和 bbsI 这两个基因没有明显的功能。bbs bbs 操作子只在甲苯生长的细胞中表达，并在转录水平上受到调控。启动子图谱显示，转录起始位点位于 bbsA 基因上游的转录起始位点。这是已知的第一个 Thauera 属中的第一个已知启动子位点。
• A new family of CoA-transferases
  作者：Johann Heider

  DOI：10.1016/s0014-5793(01)03178-7

  日期：2001.12.14

  CoA‐transferases are found in organisms from all lines of descent. Most of these enzymes belong to two well‐known enzyme families, but recent work on unusual biochemical pathways of anaerobic bacteria has revealed the existence of a third family of CoA‐transferases. The members of this enzyme family differ in sequence and reaction mechanism from CoA‐transferases of the other families. Currently known enzymes of the new family are a formyl‐CoA: oxalate CoA‐transferase, a succinyl‐CoA: (R)‐benzylsuccinate CoA‐transferase, an (E)‐cinnamoyl‐CoA: (R)‐phenyllactate CoA‐transferase, and a butyrobetainyl‐CoA: (R)‐carnitine CoA‐transferase. In addition, a large number of proteins of unknown or differently annotated function from Bacteria, Archaea and Eukarya apparently belong to this enzyme family. Properties and reaction mechanisms of the CoA‐transferases of family III are described and compared to those of the previously known CoA‐transferases.
• Succinyl-CoA:( <i>R</i> )-Benzylsuccinate CoA-Transferase: an Enzyme of the Anaerobic Toluene Catabolic Pathway in Denitrifying Bacteria
  作者：Christina Leutwein、Johann Heider

  DOI：10.1128/jb.183.14.4288-4295.2001

  日期：2001.7.15

  Anaerobic microbial toluene catabolism is initiated by addition of fumarate to the methyl group of toluene, yielding (R)-benzylsuccinate as first intermediate, which is further metabolized via beta-oxidation to benzoyl-coenzyme A (CoA) and succinyl-CoA. A specific succinyl-CoA:(R)-benzylsuccinate CoA-transferase activating (R)-benzylsuccinate to the CoA-thioester was purified and characterized from

  厌氧微生物的甲苯分解代谢是通过向甲苯的甲基中添加富马酸酯而引发的，产生的是作为第一中间体的（R）-苄基琥珀酸酯，该中间体通过β-氧化进一步代谢为苯甲酰基辅酶A（CoA）和琥珀酰-CoA。纯化了特异的琥珀酰基-CoA：（R）-苄基琥珀酸酯CoA-转移酶，将活化的（R）-苄基琥珀酸酯生成CoA-硫酯，并从Thauera aromaa进行了表征。该酶是完全可逆的，并且仅形成2-（R）-苄基琥珀酰-CoA异构体。该酶仅接受底物的一些紧密化学类似物：琥珀酸酯被马来酸酯或甲基琥珀酸酯部分替代，（R）-苄基琥珀酸酯被甲基琥珀酸酯，苄基丙二酸酯或苯基琥珀酸酯替代。与所有其他已知的CoA转移酶不同，该酶由两个相似的氨基酸序列和相似的大小（44和45 kDa）的亚基组成，并具有alpha（2）beta（2）构象。亚基与先前鉴定的甲苯诱导的bbsEF基因产物的同一性通过电喷雾质谱法测定确切质量来确定。推导的氨基