3-methyltetraacetylriboflavin | 21066-33-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 蝶啶及其衍生物
• 英文名称: 3-methyltetraacetylriboflavin
• 英文别名: 3-methyl-2',3',4',5'-tetraacetylriboflavin；[(2R,3S,4S)-2,3,4-triacetyloxy-5-(3,7,8-trimethyl-2,4-dioxobenzo[g]pteridin-10-yl)pentyl] acetate
• CAS: 21066-33-1
• 化学式: C₂₆H₃₀N₄O₁₀
• 分子量: 558.545
• InChiKey: RKGNEWRFTMKDTD-XJUOHMSHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  40
• 可旋转键数：
  13
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  171
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  3-methyltetraacetylriboflavin 在 hydroxide 作用下， 生成 alkaline earth salt of/the/ methylsulfuric acid
  参考文献：
  名称：

  Properties of 4a-hydroxy-4a,5-dihydroflavin radicals in relation to bacterial bioluminescence

  摘要：

  By means of pulse radiolysis the aqueous one-electron reduction potential and pK(a) of the 5-alkylated 4a-hydroxy-4a,5-dihydroflavin radical cation were determined. The same properties were estimated for the corresponding pseudobase radical cation of authentic flavin. The latter radical appeared not to form upon hydrolysis in water of one-electron oxidized flavin, Fl.+. By use of the present data and previously determined values the events during bacterial luminescence were quantified. The annihilation of an intimate radical ion pair is identified as the chemiexcitation step. The energy released in this process is shown to exceed by ca. 1 eV the minimum energy required for the population of the emitting state of 4a-hydroxy-4a,5-dihydroflavin. It is suggested that, initially, a low lying second excited state may be generated, which subsequently relaxes into the emitting singlet. This model also rationalizes the findings in the presence of lumazine or flavin mononucleotide (FMN). We propose that energy transfer from this state to lumazine protein or FMN-containing yellow fluorescent protein occurs by a collision mechanism in a tight complex, in competition with decay into the emitting lowest singlet of 4a-hydroxy-4a,5-dihydroflavin.

  DOI：

  10.1021/j100204a074
• 作为产物：
  描述：

  Acetic acid (1S,2S,3R)-2,3,4-triacetoxy-1-(4a-hydroperoxy-3,7,8-trimethyl-2,4-dioxo-3,4,4a,5-tetrahydro-2H-benzo[g]pteridin-10-ylmethyl)-butyl ester 以 水 为溶剂， 生成 3-methyltetraacetylriboflavin
  参考文献：
  名称：

  黄素过氧化四面体中间体的化学

  摘要：

  通过脉冲辐射分解产生了正常和 5-烷基化黄素的 4a-过氧中间体，并研究了它们衰变成黄素和相应氢过氧化物的动力学与 pH 值的关系。一方面 5-烷基化黄素阳离子的 4a-中间体和另一方面 5-protio 黄素的中性和质子催化分解非常相似。得出的结论是，正常黄素 4-过氧化物的中性分解中的决定速率步骤是沿 C(4a)-O 键的杂裂，它由作为一般酸的水催化。最初产生的物种包括 N(5)-质子化黄素阳离子、中性氢过氧化物和氢氧根离子。该过程通过黄素阳离子的快速去质子化以产生中性黄素来完成。

  DOI：

  10.1021/ja00008a051
• 作为试剂：
  描述：

  (4-氯苯基)乙醛酸 在 potassium cyanide 、 十六烷基三甲基溴化铵 、 3-methyltetraacetylriboflavin 作用下， 以 水 为溶剂， 反应 48.0h， 以0.1%的产率得到1,2-双(4-氯苯基)-2-羟基乙酮
  参考文献：
  名称：

  Coenzyme models. 20. Flavin trapping of carbanion intermediates as catalyzed by cyanide ion and cationic micelle

  摘要：

  DOI：

  10.1021/ja00527a034

文献信息

• Photocatalytic esterification under Mitsunobu reaction conditions mediated by flavin and visible light
  作者：M. März、J. Chudoba、M. Kohout、R. Cibulka

  DOI：10.1039/c6ob02770a

  日期：——

  The usefulness of flavin-based aerial photooxidation in esterification under Mitsunobu reaction conditions was demonstrated, providing aerial dialkyl azodicarboxylate recycling/generation from the corresponding dialkyl hydrazine dicarboxylate. Simultaneously, activation of triphenylphosphine (Ph3P) by photoinduced electron transfer from flavin allows azo-reagent-free esterification. An optimized system

  证明了基于黄素的空中光氧化在Mitsunobu反应条件下进行酯化反应中的有用性，从而提供了从相应的二烷基肼二羧酸二乙酯中回收/生成空中二烷基偶氮二羧酸酯的方法。同时，通过黄素的光诱导电子转移激活三苯膦（Ph 3 P）可以使无偶氮试剂进行酯化。已显示使用3-乙酸甲基黄酮黄素四乙酸酯（10％），氧气（末端氧化剂），可见光（450 nm），Ph 3 P和二羧酸肼二甲酸二烷基酯（10％）的优化系统可提供各种醇的高效立体选择性偶联和酸变成酯，并保留构型。
• Photooxidation of Benzyl Alcohols with Immobilized Flavins
  作者：Harald Schmaderer、Petra Hilgers、Robert Lechner、Burkhard König

  DOI：10.1002/adsc.200800576

  日期：2009.1

  Benzyl alcohols are oxidized cleanly and efficiently to the corresponding aldehydes under irradiation using flavin photocatalysts and aerial oxygen as the terminal oxidant in homogeneous aqueous solution. Turnover frequencies (TOF) of more than 800 h−1 and turnover numbers (TON) of up to 68 were obtained. Several flavin photocatalysts with fluorinated or hydrophobic aliphatic chains were immobilized

  使用黄素光催化剂和空气中的氧气作为末端氧化剂，在均匀的水溶液中，在照射下将苄醇清洁有效地氧化为相应的醛。超过800 h -1的周转频率（TOF）营业额（TON）达到68。将几种具有氟化或疏水性脂肪族链的黄素光催化剂固定在固体载体上，例如氟硅胶，反相硅胶或截留在聚乙烯粒料中。研究了非均相光催化剂对水中不同苄醇氧化的催化效率，并将其与类似的均相反应进行了比较。除去非均相光催化剂会立即停止反应转化，这表明固定化的黄素是催化活性物质。固定的催化剂是稳定的，如果与相应的均相系统相比，则保持其反应性，并且容易从反应混合物中除去并重复使用。TOF长达26 h -1异质黄素光催化剂可能具有280的TON和最多3个反应周期而不会失去活性。
• Azodicarboxylate-free esterification with triphenylphosphine mediated by flavin and visible light: method development and stereoselectivity control
  作者：Michal März、Michal Kohout、Tomáš Neveselý、Josef Chudoba、Dorota Prukała、Stanislaw Niziński、Marek Sikorski、Gotard Burdziński、Radek Cibulka

  DOI：10.1039/c8ob01822g

  日期：——

  single-electron oxidation. Unexpected stereoselectivity control by the solvent was observed, allowing switching from inversion to retention of configuration during esterification of (S)- or (R)-1-phenylethanol; for example with phenylacetic acid, the ratio shifting from 10 : 90 (retention : inversion) in trifluoromethylbenzene to 99.9 : 0.1 in acetonitrile. Our method uses nitrobenzene to regenerate the flavin

  被各种亲电试剂（例如重氮羧酸烷基酯）活化的三苯膦（Ph 3 P）代表了酯化反应和其他亲核取代反应的有效介质。我们在这里报告了一种使用黄素催化剂（3-甲基核黄素四乙酸盐），三苯膦和可见光（448 nm）的无氮杂试剂的方法，该方法可以使芳香族和脂肪族羧酸与醇类有效地酯化。机理研究证实从三苯基膦的Ph的形成该光诱导电子转移到兴奋黄素3 P˙ +是在催化循环的关键步骤。这允许通过的Ph的醇的反应而产生的反应物种alkoxyphosphonium 3 P˙+然后进行单电子氧化。观察到通过溶剂的意外的立体选择性控制，使得在（ S）-或（ R）-1-苯基乙醇的酯化过程中可以从转化转变为保留构型。例如，使用苯乙酸时，该比率从三氟甲基苯中的10:90（保留：转化）变为乙腈中的99.9：0.1。我们的方法使用硝基苯再生黄素光催化剂。黄素再氧化的这种新方法也已在苄醇氧化中得到了成功证明，这是黄素介导的光氧化中的“标准”过程。
• Riboflavin derivatives for enhanced photodynamic activity against Leishmania parasites
  作者：Alexandre Vieira Silva、Almudena López-Sánchez、Helena Couto Junqueira、Luis Rivas、Mauricio S. Baptista、Guillermo Orellana

  DOI：10.1016/j.tet.2014.11.072

  日期：2015.1

  Riboflavin derivatives with various substituents (O-acyl, N-methyl, N-alkylcarboxyalkyl or N-alkyl(trialkyl) ammonium) have been prepared and spectroscopically characterized (absorption, emission and fluorescence quantum yields). Their quantum yields of photosensitized singlet molecular oxygen production (Phi(Delta) 0.24-0.58) and octanol/water partition coefficients (P-ow <= 0.01-11) were measured. Preliminary studies indicate that all derivatives display higher phototoxicity against the human protozoan parasite Leishmania than the parent riboflavin, with negligible toxicity in the absence of light. Their photodynamic action shows a higher correlation with Pow than with Phi(Delta), opening up their potential application to cutaneous diseases treatment. (C) 2014 Elsevier Ltd. All rights reserved.