(3E,4Z,10Z,15Z)-18-ethyl-3-ethylidene-1,2,3,19,22,24-hexahydro-2,7,13,17-tetramethyl-1,19-dioxo-21H-biline-8,12-dipropanoic acid

• 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: (3E,4Z,10Z,15Z)-18-ethyl-3-ethylidene-1,2,3,19,22,24-hexahydro-2,7,13,17-tetramethyl-1,19-dioxo-21H-biline-8,12-dipropanoic acid
• 英文别名: phycocyanobilin
• 化学式: C₃₃H₃₈N₄O₆
• 分子量: 586.688
• InChiKey: INPDFIMLLXXDOQ-ZZEPTHGGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.11
• 重原子数：
  43.0
• 可旋转键数：
  10.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  160.95
• 氢给体数：
  5.0
• 氢受体数：
  5.0

反应信息

• 作为产物：
  描述：

  4-(1-bromoethyl)-1-t-butoxycarbonyl-1,5-dihydro-3-methyl-5-tosyl-2H-pyrrol-2-one 在 aluminum amalgam 、 三丁基膦 、 硫酸 、 potassium tert-butylate 、 sodium acetate 、 4-甲基苯磺酸吡啶 、 三氟乙酸 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 水 为溶剂， 反应 9.17h， 生成 (3E,4Z,10Z,15Z)-18-ethyl-3-ethylidene-1,2,3,19,22,24-hexahydro-2,7,13,17-tetramethyl-1,19-dioxo-21H-biline-8,12-dipropanoic acid
  参考文献：
  名称：

  Efficient Construction of A,B-Rings Component for Syntheses of Phycocyanobilin and Its Derivative

  摘要：

  该方法包括 4-(1-甲氧基乙基)-3-甲基-5-对甲苯磺酰基-1,5-二氢-2H-吡咯-2-酮和 2-甲酰基吡咯衍生物在 nBu3P 和碱存在下的 Wittig 型新偶联反应，然后用铝汞齐还原并进行酸处理。

  DOI：

  10.1246/cl.1998.1227

文献信息

• An Efficient Method to Construct the A,B-Rings Component toward Total Syntheses of Phycocyanobilin and Its Derivative as a Photoprobe
  作者：Krishanthi Padmarani Jayasundera、Hideki Kinoshita、Katsuhiko Inomata

  DOI：10.1246/bcsj.73.497

  日期：2000.2

  Total syntheses of phycocyanobilin and its derivative bearing a photoreactive group at the D-ring were accomplished by developing a new and efficient method for the construction of A,B-rings component, which consists of the Wittig-type new coupling reaction of 4-(1-methoxyethyl or 1-tosylethyl)-3-methyl-5-tosyl-1,5-dihydro-2H-pyrrol-2-one and a 2-formyl pyrrole derivative in the presence of nBu3P and a base, followed by reduction with aluminum amalgam and a subsequent acid or base treatment.

  通过开发一种新颖且高效的方法构建A、B环部分，成功完成了藻蓝蛋白胆色素及其在D环上具有光反应基团的衍生物的总合成。该方法包括在nBu3P和碱存在下，4-(1-甲氧基乙基或1-托烯乙基)-3-甲基-5-托烯-1,5-二氢-2H-吡咯烷-2-酮与2-呋喃基吡咯衍生物的Wittig型新偶联反应，随后用铝齐聚物还原，并进行酸或碱处理。
• Efficient Synthesis of B- and C-Rings Components of Phycobilin Derivatives for Structure/Function Analysis of Phytochrome
  作者：Atsuko Ohta、Daisuke Sawamoto、Krishanthi Padmarani Jayasundera、Hideki Kinoshita、Katsuhiko Inomata

  DOI：10.1246/cl.2000.492

  日期：2000.5

  B- and C-Rings components of phycobilin derivatives were efficiently prepared starting from the corresponding lactones. This synthetic method made it possible to prepare not only phycocyanobilin (PCB), but also PCB derivatives having butanoic acid side chain(s) instead of propanoic one(s), regioselectively monoesterified PCB derivatives at C8 or C12, and regioisomers of PCB with respect to methyl and propanoic acid substituents of B- and C-rings for the first time toward the structure/function analysis of phytochrome.

  从相应的内酯开始，高效地制备出了植物纤维素衍生物的 B 环和 C 环成分。这种合成方法不仅可以制备植物花青素（PCB），还可以制备具有丁酸侧链而非丙酸侧链的 PCB 衍生物、C8 或 C12 处的区域选择性单酯化 PCB 衍生物，以及 PCB 与 B 环和 C 环的甲基和丙酸取代基的区域异构体，从而首次实现了对植物色素的结构/功能分析。
• Total Syntheses of (±)-Phycocyanobilin and Its Derivatives Bearing a Photoreactive Group at D-ring
  作者：Takashi Kakiuchi、Hirohide Kato、Krishanthi Padmarani Jayasundera、Taijiro Higashi、Kazuhiko Watabe、Daisuke Sawamoto、Hideki Kinoshita、Katsuhiko Inomata

  DOI：10.1246/cl.1998.1001

  日期：1998.10

  (±)-Phycocyanobilin and its derivatives bearing a photoreactive group at D-ring were first synthesized by the development of a new and convenient method for the preparation of A-ring, transesterification for propanoic acid side-chains of the pyrrole derivative common to B- and C-rings, and deprotection of allyl ester side-chains with a palladium catalyst to avoid migration of exocyclic olefin of A-ring.

  (±)-藻蓝胆素及其在 D 环上带有光反应性基团的衍生物首先是通过开发一种新的方便的方法来合成的，该方法用于制备 A 环，对 B 共有的吡咯衍生物的丙酸侧链进行酯交换- 和 C 环，以及使用钯催化剂对烯丙酯侧链进行脱保护，以避免 A 环的环外烯烃迁移。
• An Efficient Method for the Conversion of 2-Bromo-5-tosylpyrroles to the Corresponding 5-Tosylpyrrolinones as the D-Ring of Phycocyanobilin Derivatives
  作者：Shuzo Takeda、Krishanthi Padmarani Jayasundera、Takashi Kakiuchi、Hideki Kinoshita、Katsuhiko Inomata

  DOI：10.1246/cl.2001.590

  日期：2001.6

  2-Bromo-5-tosylpyrroles were efficiently converted to the corresponding 5-tosylpyrrolinones as the D-ring of phycocyanobilin (PCB) derivatives by treating with DMSO and Zn in TFA in the presence of a catalytic amount of iodine. PCB derivatives modified at the D-ring were prepared in free acid forms employing the resulting 5-tosylpyrrolinones toward structure/function analysis of phytochrome.

  在一定量的碘催化下，在反式脂肪酸中用二甲基亚砜和锌处理 2-溴-5-对甲苯磺酰基吡咯烷，可有效地将其转化为相应的 5-对甲苯磺酰基吡咯烷酮，作为植物花青素（PCB）衍生物的 D 环。利用得到的 5-对甲苯磺酰基吡咯烷酮对植物色素进行结构/功能分析。
• Total Syntheses of Phycocyanobilin Derivatives Bearing a Modified A-Ring toward the Structure/Function Analysis of Phytochrome
  作者：Daisuke Sawamoto、Hiroshi Nakamura、Hideki Kinoshita、Shuhei Fujinami、Katsuhiko Inomata

  DOI：10.1246/cl.2000.1398

  日期：2000.12

  Phycocyanobilin (PCB) derivatives bearing a modified A-ring, including 3,3′-dihydrogenated PCB derivatives, were efficiently synthesized in free acid forms by applying our original methods for the preparation of A-, A/B-, and C/D-ring components toward the structure/function analysis of phytochrome.

  为了对植物色素进行结构/功能分析，我们采用独创的 A-环、A/B-环和 C/D 环成分制备方法，高效合成了具有修饰 A 环的植物花青素（PCB）衍生物，包括 3,3′-二氢化 PCB 衍生物的游离酸形式。