nickel methyl pyropheophorbide-a

• 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: nickel methyl pyropheophorbide-a
• 英文别名: (21S,22S)-16-ethenyl-11-ethyl-22-(3-methoxy-3-oxopropyl)-12,17,21,26-tetramethyl-23,24,25-triaza-7-azanidahexacyclo[18.2.1.15,8.110,13.115,18.02,6]hexacosa-1(23),2(6),4,8(26),9,11,13(25),14,16,18(24),19-undecaen-4-olate;nickel(2+)
• 化学式: C₃₄H₃₄N₄NiO₃
• 分子量: 605.359
• InChiKey: DRMQGULWZLLLSH-COBSGTNCSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  6.75
• 重原子数：
  42
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  70.1
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  nickel methyl pyropheophorbide-a 在 palladium on activated charcoal 作用下， 以 四氢呋喃 、 丙酮 为溶剂， 以90%的产率得到nickel methyl mesopyropheophorbide-a
  参考文献：
  名称：

  （细菌）叶绿素衍生物中的3-取代基的修饰以制备3-乙基化，甲基化和未取代的（镍）焦脱镁叶绿酸及其光学性质

  摘要：

  通过修饰带有3的天然（细菌）叶绿素来制备在3位上具有乙基的甲基间苯二酚a-，其31-脱甲基类似物（3-甲基同系物）及其31-脱乙基类似物（3-未取代的二氢卟酚）。 -乙烯基，甲酰基，乙酰基和1-羟乙基。这些合成的3-（未）取代的叶绿素衍生物及其镍配合物可能是（细菌）叶绿素降解成化学稳定的卟啉类化合物的中间体。测量溶液中分解代谢候选物的光学性质（可见吸收，圆二色性和荧光发射），并研究取代效果。

  DOI：

  10.1021/jo300442t
• 作为产物：
  描述：

  methyl pyropheophorbide a 在 nickel diacetate 作用下， 以 甲醇 、 氯仿 为溶剂， 生成 nickel methyl pyropheophorbide-a
  参考文献：
  名称：

  Specific coupling between the 13-keto carbonyl and chlorin skeletal vibrational modes of synthetic 131-18O-(un)labelled metallochlorophyll derivatives

  摘要：

  Metal complexes of methyl 13(1)-O-18-labelled pyropheophorbide-a 1-M-O-18 (M = Zn, Cu and Ni) were prepared by metallation of the O-18-labelled free base (1-O-18) and O-18-labelling of unlabelled nickel complex (1-Ni). The FT-IR spectra of 1-Zn and 1-Zn-O-18 in CH2Cl2 showed that the 13-keto carbonyl stretching vibration mode moved to about a 30-cm(-1) lower wavenumber by O-18-labelling of the 13(1)-oxo moiety. in 1-Cu-O-18 and 1-Ni-O-18, the 13-C=O-18 stretching modes were close to the highest-energy wavenumber mode of chlorin skeletal C-C/C-N vibrations at around 1650cm(-1) and they were coupled in CH2O2 to give two split IR bands (Fermi resonance). A similar coupling was observed in the resonance Raman scattering of 1-Ni-O-18 in the solid state. The hydrogen-bonded 13-C=O-16 vibration mode of 1-Ni similarly coupled with the skeletal C-C/C-N mode in CCl4 containing 1% (v/v) 1,1,1,3,3,3-hexafluoro-2-propanol, while such a coupling was not observed in a neat CCl4 Solution of 1-Ni possessing the 13-C=O-16 free from any interaction. The skeletal C-C/C-N band selectively coupled with the 13-C=O, not with the 3-C=O, when the difference in their peak maxima was less than 20 cm(-1). (c) 2008 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.saa.2008.09.016

文献信息

• Synthesis of Sedimentary Porphyrin-like Chlorophyll-<i>a</i> Derivatives Lacking the 3-Substituent
  作者：Marie Doi、Hitoshi Tamiaki

  DOI：10.1246/cl.190911

  日期：2020.3.5

  Nickel methyl 3-devinyl-pyropheophorbide-a was unexpectedly synthesized by chemical modification of naturally occurring chlorophyll-a. The removal of the 3-substituents proceeded by heating in an a...

  通过天然存在的叶绿素-a 的化学修饰，意外地合成了甲基镍 3-二乙烯-焦脱镁叶绿素-a。3-取代基的去除是通过在一个...
• Ene-thiol reaction of <font>C</font>3-vinylated chlorophyll derivatives in the presence of oxygen: synthesis of <font>C</font>3-formyl-chlorins under mild conditions
  作者：Takanori Fukusumi、Natsuki Takei、Yubi Tateno、Takuya Aoki、Ai Ando、Kouhei Kozakai、Hiroko Shima、Tadashi Mizoguchi、Satoshi Ito、Tsukasa Ikeda、Hitoshi Tamiaki、Toru Oba

  DOI：10.1142/s1088424613500983

  日期：2013.12

  Reactions of thiol with the C 3-vinyl group of various chlorophyll (Chl) derivatives were examined. The reactions resemble thiol-olefin co-oxidation, except that the vinyl C = C double bond was cleaved to afford a formyl group without any transition metal catalyst, and that the simple anti-Markovnikov adduct of thiol to olefin was obtained as a minor product. Peripheral substituents of Chl derivatives little affected the reaction, while the central metal atom of the chlorin macrocycle influenced the composition of the products. Oxygen and acid dissolved in the reaction mixture can facilitate the oxidation. Sufficiently mild conditions in this regioselective oxidation at the C 3¹-position are significant in bioorganic chemistry.

  研究了硫醇与各种叶绿素（Chl）衍生物的 C 3-乙烯基的反应。这些反应类似于硫醇与烯烃的共氧化反应，只是乙烯基 C = C 双键在没有任何过渡金属催化剂的情况下被裂解以产生甲酰基，而且硫醇与烯烃的简单反马尔科夫尼科夫加合物作为次要产物被获得。Chl 衍生物的外围取代基对反应的影响很小，而氯素大环的中心金属原子则会影响产物的组成。溶解在反应混合物中的氧气和酸可促进氧化。在这种 C 31 位的区域选择性氧化反应中，足够温和的条件在生物有机化学中具有重要意义。
• Metallation of a cyclic chlorophyll hetero-dyad, and the optical properties of synthetic metallo-dyads
  作者：Hitoshi Tamiaki、Nobuo Kosaka、Yusuke Kinoshita

  DOI：10.1007/s11164-012-0644-4

  日期：2013.1

  A cyclic chlorophyll hetero-dyad 1-H2H2, prepared by double ester linking of two structurally different pyropheophorbide-a moieties through 3-CH2OCO-132′ and 172-COOCH2-3′, was metallated with zinc and copper to give mono and di-metallated complexes 1-MH2 or 1-H2M and 1-MM. The metallation proceeded stepwise and regioselectively, with predominant synthesis of one of the two mono-metallated complexes 1-MH2 as intermediate. The di-zinc complex produced, 1-ZnZn, was demetallated exclusively via the same mono-zinc complex 1-ZnH2 as was the major intermediate during metallation. Visible and/or circular dichroism spectra of 1-H2H2, 1-MH2, 1-H2M, and 1-MM (M = Ni, Cu, or Zn) were measured in organic solvents. Intramolecular interaction of chlorin chromophores is discussed and compared with that of the corresponding monomeric species.

  环状叶绿素杂二元体 1-H2H2，由两个结构不同的焦脱镁叶绿酸-a 部分通过 3-CH2OCO-132' 和 172-COOCH2-3' 双酯连接制备，用锌和铜金属化，得到单和二-金属化配合物1-MH2或1-H2M和1-MM。金属化以区域选择性的方式逐步进行，主要合成了两种单金属化配合物 1-MH2 之一作为中间体。所产生的二锌络合物 1-ZnZn 完全通过与金属化过程中主要中间体相同的单锌络合物 1-ZnH2 脱金属。在有机溶剂中测量 1-H2H2、1-M​​H2、1-H2M 和 1-MM（M = Ni、Cu 或 Zn）的可见光和/或圆二色光谱。讨论了二氢卟酚发色团的分子内相互作用，并与相应单体的分子内相互作用进行了比较。
• BciC‐Catalyzed C13 ² ‐Demethoxycarbonylation of Metal Pheophorbide  <i>a</i> Alkyl Esters
  作者：Mitsuaki Hirose、Misato Teramura、Jiro Harada、Hitoshi Tamiaki

  DOI：10.1002/cbic.201900745

  日期：2020.5.15

  propionate residues and central metals were examined by using the BciC enzyme derived from one green sulfur bacteria species, Chlorobaculum tepidum. The BciC enzymatic reactions of zinc pheophorbide a alkyl esters were gradually suppressed with an increase of the alkyl chain length in the C17-propionate residue (from methyl to pentyl esters) and finally the hexyl ester became inactive for the BciC reaction

  细菌叶绿素c分子自聚集形成大量的寡聚体，位于绿体的核心部分，绿体是绿色光合细菌的主要光收集天线系统。在细菌叶绿素c的生物合成途径中，BciC酶催化去除叶绿素a的C132-甲氧基羰基，该叶绿素a在C17位具有游离丙酸酯残基，且镁离子为中心金属。通过使用衍生自一种绿色硫细菌物种Tekpidum的BciC酶，对具有各种丙酸烷基酯残基和中心金属的叶绿素a衍生物进行了体外C132-脱甲氧基羰基化反应。脱镁变色锌a烷基酯的BciC酶促反应随着C17-丙酸酯残基中烷基链长度的增加（从甲基到戊酯）而逐渐被抑制，最后己酯对BciC反应失去活性。尽管不仅锌，而且镍和铜络合物都被BciC酶脱甲氧基羰基化，但反应很大程度上取决于中心金属的配位能力：Zn> Ni> Cu。上述底物特异性表明，BciC酶不会直接结合至叶绿素a的羧基，但会与其中央镁结合形成BciC与叶绿素a的立体定向复合物，从而得到缺少（132 R）的焦叶绿素a。
• Direct C–H borylation of vinylporphyrins <i>via</i> copper catalysis
  作者：Evgeny S. Belyaev、Grigory L. Kozhemyakin、Vladimir S. Tyurin、Victoria V. Frolova、Ivan S. Lonin、Gelii V. Ponomarev、Aleksey K. Buryak、Ilya A. Zamilatskov

  DOI：10.1039/d1ob02005f

  日期：——

  developed based on the copper catalyzed vinylic C–H activation. Ni(II) complexes of meso- and β-vinylporphyrinoids have been transformed to the corresponding pinacolboronated derivatives with good yields and high (E)-stereoselectivity. The method provides an easy and direct access to the valuable synthons which were shown to act as nucleophylic partners in the Suzuki cross-coupling building tetrapyrrole

  基于铜催化的乙烯基 C-H 活化，已开发出一种乙烯基取代的卟啉（卟啉和二氢卟吩）直接硼化的方法。内消旋和 β-乙烯基卟啉的Ni( II ) 配合物已被转化为相应的频哪醇硼化衍生物，具有良好的收率和高 ( E )-立体选择性。该方法提供了一种简单而直接的方法来获得有价值的合成子，这些合成子在 Suzuki 交叉偶联构建四吡咯衍生物中通过碳-碳双键与 π 共轭形成亲核伙伴。