biliverdin IXα dimethyl ester

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: biliverdin IXα dimethyl ester
• 化学式: C₃₅H₃₈N₄O₆
• 分子量: 610.71
• InChiKey: UYHZQOJAPATOSQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.98
• 重原子数：
  45.0
• 可旋转键数：
  11.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  138.95
• 氢给体数：
  3.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  biliverdin IXα dimethyl ester 在 sodium hydroxide 作用下， 以 甲醇 、 水 为溶剂， 以87 %的产率得到biliverdin IXα
  参考文献：
  名称：

  胆红素氧化产物的合成平台

  摘要：

  胆红素是血红素分解代谢的主要产物。高浓度的色素具有神经毒性，但稍微升高浓度则有益。作为一种有效的抗氧化剂，胆红素在体内发生氧化转化并产生各种氧化片段。它们的形成机制、内在的生物活性以及在人类病理生理学中的潜在作用尚不清楚。降解方法已用于获取胆红素氧化产物的样品以供研究。在这里，我们报告了一种补充的、全合成的制备方法。我们的策略利用母体四环颜料中的重复取代模式。设计并有效合成了功能化的可偶联γ-内酯、γ-内酰胺和吡咯单环结构单元。随后的模块化组合，在金属催化的硼化和交叉偶联化学的支持下，转化为结构多样的胆红素氧化产物（BOX、propentdyopents和biopyrrins）的简洁组装。据报道，发现了一种新的生物比林 A 光异构体，名为 lumipyrrin。足够纯度和数量的合成胆红素氧化产物将支持未来的体外和体内研究。

  DOI：

  10.1021/jacs.3c11778
• 作为产物：
  描述：

  bilirubin IXα 在 盐酸 、 1-羟基苯并三唑 、 O-(1H-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate 、 N,N-二异丙基乙胺 作用下， 以 水 、 二甲基亚砜 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.08h， 生成 biliverdin IXα dimethyl ester
  参考文献：
  名称：

  Biliverdin Amides Reveal Roles for Propionate Side Chains in Bilin Reductase Recognition and in Holophytochrome Assembly and Photoconversion

  摘要：

  Linear tetrapyrroles (bilins) perform important antioxidant and light-harvesting functions in cells from bacteria to humans. To explore the role of the propionate moieties in bilin metabolism, we report the semisynthesis of mono- and diamides of biliverdin IX alpha and those of its non-natural XIII alpha isomer. Initially, these were examined as substrates of two types of NADPH-dependent biliverdin reductase, BVR and BvdR, and of the representative ferredoxin-dependent bilin reductase, phycocyanobilin:ferredoxin oxidoreductase (PcyA). Our studies indicate that the NADPH-dependent biliverdin reductases are less accommodating to amidation of the propionic acid side chains of biliverdin IX alpha than PcyA, which does not require free carboxylic acid side chains to yield its phytobilin product, phycocyanobilin. Bilin amides were also assembled with BV-type and phytobilin-type apophytochromes, demonstrating a role for the 8-propionate in the formation of the spectroscopically native P-r dark states of these biliprotein photosensors. Neither ionizable propionate side chain proved to be essential to primary photoisomerization for both classes of phytochromes, but an unsubstituted 12-propionate was required for full photointerconversion of phytobilin-type phytochrome Cph1. Taken together, these studies provide insight into the roles of the ionizable propionate side chains in substrate discrimination by two bilin reductase families while further underscoring the mechanistic differences between the photoconversions of BV-type and phytobilin-type phytochromes.

  DOI：

  10.1021/bi100756x

文献信息

• 一种用胆绿素Ⅸα二酯制备高含量胆红素Ⅸα 的方法
  申请人：百顺药业有限公司

  公开号：CN109535057B

  公开（公告）日：2020-03-10

  本发明公开了一种用胆绿素Ⅸα二酯制备高含量胆红素Ⅸα的方法。属于胆红素Ⅸα制备领域。该方法包括如下步骤(先水解后还原路线)：在胆绿素Ⅸα二酯的醇溶液中，滴加氢氧化钠的甲醇溶液，加入水后水解，然后用弱酸调节pH到4～5，旋转蒸发除溶剂，水洗除无机盐，真空干燥后得到胆绿素Ⅸα。在胆绿素Ⅸα的醇溶液中，加入游离基清除剂(稳定剂)，加入还原剂硼氢化物，在还原反应结束时，立即加入酮分解过量的还原剂，然后用弱酸调节pH到4～5，旋转蒸发除溶剂，然后水洗，甲醇‑氯仿精制后得到含量超97％的胆红素Ⅸα。该方法不需要色谱分离，反应条件温和，成本低，操作方便，适于工业化大生产。
• AN EFFICIENT ONE-STEP CONVERSION OF BILIVERDINS TO 14-FORMYLTRIPYRRINONES
  作者：Peng Wang、Yi Zhang、Qingqi Chen、Jin Shi Ma

  DOI：10.1080/00304940209355755

  日期：2002.4
• Saito, Setsuo; Itano, Harvey A., Journal of the Chemical Society. Perkin transactions I
  作者：Saito, Setsuo、Itano, Harvey A.

  DOI：——

  日期：——
• Biliverdin Amides Reveal Roles for Propionate Side Chains in Bilin Reductase Recognition and in Holophytochrome Assembly and Photoconversion
  作者：Lixia Shang、Nathan C. Rockwell、Shelley S. Martin、J. Clark Lagarias

  DOI：10.1021/bi100756x

  日期：2010.7.27

  Linear tetrapyrroles (bilins) perform important antioxidant and light-harvesting functions in cells from bacteria to humans. To explore the role of the propionate moieties in bilin metabolism, we report the semisynthesis of mono- and diamides of biliverdin IX alpha and those of its non-natural XIII alpha isomer. Initially, these were examined as substrates of two types of NADPH-dependent biliverdin reductase, BVR and BvdR, and of the representative ferredoxin-dependent bilin reductase, phycocyanobilin:ferredoxin oxidoreductase (PcyA). Our studies indicate that the NADPH-dependent biliverdin reductases are less accommodating to amidation of the propionic acid side chains of biliverdin IX alpha than PcyA, which does not require free carboxylic acid side chains to yield its phytobilin product, phycocyanobilin. Bilin amides were also assembled with BV-type and phytobilin-type apophytochromes, demonstrating a role for the 8-propionate in the formation of the spectroscopically native P-r dark states of these biliprotein photosensors. Neither ionizable propionate side chain proved to be essential to primary photoisomerization for both classes of phytochromes, but an unsubstituted 12-propionate was required for full photointerconversion of phytobilin-type phytochrome Cph1. Taken together, these studies provide insight into the roles of the ionizable propionate side chains in substrate discrimination by two bilin reductase families while further underscoring the mechanistic differences between the photoconversions of BV-type and phytobilin-type phytochromes.
• A Platform for the Synthesis of Oxidation Products of Bilirubin
  作者：Taufiqueahmed Mujawar、Petr Sevelda、Dominik Madea、Petr Klán、Jakub Švenda

  DOI：10.1021/jacs.3c11778

  日期：2024.1.17

  borylation and cross-coupling chemistries, translated into the concise assembly of the structurally diverse bilirubin oxidation products (BOXes, propentdyopents, and biopyrrins). The discovery of a new photoisomer of biopyrrin A named lumipyrrin is reported. Synthetic bilirubin oxidation products made available in sufficient purity and quantity will support future in vitro and in vivo investigations.

  胆红素是血红素分解代谢的主要产物。高浓度的色素具有神经毒性，但稍微升高浓度则有益。作为一种有效的抗氧化剂，胆红素在体内发生氧化转化并产生各种氧化片段。它们的形成机制、内在的生物活性以及在人类病理生理学中的潜在作用尚不清楚。降解方法已用于获取胆红素氧化产物的样品以供研究。在这里，我们报告了一种补充的、全合成的制备方法。我们的策略利用母体四环颜料中的重复取代模式。设计并有效合成了功能化的可偶联γ-内酯、γ-内酰胺和吡咯单环结构单元。随后的模块化组合，在金属催化的硼化和交叉偶联化学的支持下，转化为结构多样的胆红素氧化产物（BOX、propentdyopents和biopyrrins）的简洁组装。据报道，发现了一种新的生物比林 A 光异构体，名为 lumipyrrin。足够纯度和数量的合成胆红素氧化产物将支持未来的体外和体内研究。