pyriculariol

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: pyriculariol
• 英文别名: 2-[(1E,3E,5R,6S)-5,6-dihydroxyhepta-1,3-dienyl]-6-hydroxybenzaldehyde
• 化学式: C₁₄H₁₆O₄
• 分子量: 248.279
• InChiKey: UPAHLPUINKDRNK-BZUCXLHXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  77.8
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  pyriculariol 在 sodium periodate 、 对甲苯磺酸 作用下， 以 1,4-二氧六环 、 水 为溶剂， 生成 2-Hydroxy-6-((1E,3E)-5-oxo-penta-1,3-dienyl)-benzaldehyde
  参考文献：
  名称：

  Nukina, Manabu; Sassa, Takeshi; Ikeda, Michimasa, Agricultural and Biological Chemistry, 1981, vol. 45, # 9, p. 2161 - 2162

  摘要：

  DOI：
• 作为产物：
  描述：

  3,4-二-O-乙酰-1,5-酐-2,6-双脱氧-L-阿拉伯-己-1-糖醇 在 吡啶 、 manganese(IV) oxide 、 正丁基锂 、 硫酸 、 乙酸酐 、 potassium carbonate 、 mercury(II) sulfate 、 溶剂黄146 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 正己烷 、 水 、 甲苯 为溶剂， 反应 39.0h， 生成 pyriculariol
  参考文献：
  名称：

  Synthesis of (12R,13S)-pyriculariol and (12R,13S)-dihydropyriculariol revealed that the rice blast fungus, Pyricularia oryzae, produces these phytotoxins as racemates

  摘要：

  使用Wittig反应或微波辅助的Stille偶联反应作为关键步骤，合成了米瘟病菌Pyricularia oryzae分离的植物毒素pyriculariol（1）和dihydropyriculariol（2）的假定天然（12R，13S）对映体。合成表明，天然1和2是外消旋体。在水稻叶上进行叶面喷施试验表明，水杨醛核心和侧链均对植物毒性活性必不可少。当使用旋转摇床进行孵育时，真菌会产生光学活性的植物毒素，但是使用通气罐发酵器培养时则产生外消旋体。

  DOI：

  10.1093/bbb/zbaa002

文献信息

• First synthesis and absolute configuration of (−)-pyriculariol, a phytotoxin isolated from rice blast fungus, Magnaporthe grisea. Use of microwave irradiation to control Stille coupling reaction products
  作者：Ayaka Sasaki、Koji Tanaka、Yuuki Sato、Shigefumi Kuwahara、Hiromasa Kiyota

  DOI：10.1016/j.tetlet.2009.05.109

  日期：2009.8

  First total synthesis of (−)-pyriculariol, a phytotoxin isolated from rice blast fungus, Magnaporthe grisea, was achieved to determine the absolute configuration of the natural product to be 5′R,6′S. The key step was Stille coupling reaction using microwave irradiation from −78 °C to control the reaction.

  第一的全合成（ - ） - pyriculariol，从稻瘟病菌，分离的植物毒素稻瘟病菌，达到确定的天然产物的绝对构型为5' - [R，6'小号。关键步骤是使用-78°C的微波辐射进行的斯蒂勒偶联反应，以控制反应。
• Unravelling the biosynthesis of pyriculol in the rice blast fungus Magnaporthe oryzae
  作者：Stefan Jacob、Thomas Grötsch、Andrew J Foster、Anja Schüffler、Patrick H Rieger、Louis P Sandjo、Johannes C Liermann、Till Opatz、Eckhard Thines

  DOI：10.1099/mic.0.000396

  日期：2017.4.1

  Pyriculol was isolated from the rice blast fungus Magnaporthe oryzae and found to induce lesion formation on rice leaves. These findings suggest that it could be involved in virulence. The gene MoPKS19 was identified to encode a polyketide synthase essential for the production of the polyketide pyriculol in the rice blast fungus M. oryzae. The transcript abundance of MoPKS19 correlates with the biosynthesis rate of pyriculol in a time-dependent manner. Furthermore, gene inactivation of MoPKS19 resulted in a mutant unable to produce pyriculol, pyriculariol and their dihydro derivatives. Inactivation of a putative oxidase-encoding gene MoC19OXR1, which was found to be located in the genome close to MoPKS19, resulted in a mutant exclusively producing dihydropyriculol and dihydropyriculariol. By contrast, overexpression of MoC19OXR1 resulted in a mutant strain only producing pyriculol. The MoPKS19 cluster, furthermore, comprises two transcription factors MoC19TRF1 and MoC19TRF2, which were both found individually to act as negative regulators repressing gene expression of MoPKS19. Additionally, extracts of ΔMopks19 and ΔMoC19oxr1 made from axenic cultures failed to induce lesions on rice leaves compared to extracts of the wild-type strain. Consequently, pyriculol and its isomer pyriculariol appear to be the only lesion-inducing secondary metabolites produced by M. oryzae wild-type (MoWT) under these culture conditions. Interestingly, the mutants unable to produce pyriculol and pyriculariol were as pathogenic as MoWT, demonstrating that pyriculol is not required for infection.

  吡菌醇是从水稻稻瘟病菌中分离出来的，发现它能够诱导水稻叶片形成病斑。这些发现表明它可能与致病性有关。MoPKS19基因被确定为编码一种多聚酮合成酶，该酶对于水稻稻瘟病菌中多聚酮吡菌醇的产生至关重要。MoPKS19的转录丰度与吡菌醇的生物合成速率呈时间依赖性相关。此外，MoPKS19基因的失活导致突变体无法产生吡菌醇、吡菌醇及其二氢衍生物。假定的氧化酶编码基因MoC19OXR1的失活导致突变体仅产生二氢吡菌醇和二氢吡菌醇。相比之下，MoC19OXR1的过度表达导致突变株仅产生吡菌醇。此外，MoPKS19簇包括两个转录因子MoC19TRF1和MoC19TRF2，它们都被单独发现作为负调控因子抑制MoPKS19的基因表达。此外，与野生型菌株的提取物相比，由无菌培养物制成的ΔMopks19和ΔMoC19oxr1的提取物未能诱导水稻叶片形成病斑。因此，吡菌醇及其异构体吡菌醇似乎是野生型（MoWT
• Synthesis of (12<i>R</i>,13<i>S</i>)-pyriculariol and (12<i>R</i>,13<i>S</i>)-dihydropyriculariol revealed that the rice blast fungus, <i>Pyricularia oryzae</i>, produces these phytotoxins as racemates
  作者：Yuta Nagashima、Ayaka Sasaki、Ryoya Hiraoka、Yuko Onoda、Koji Tanaka、Zi-Yi Wang、Atsuki Kuwana、Yuki Sato、Yuji Suzuki、Minoru Izumi、Shigefumi Kuwahara、Manabu Nukina、Hiromasa Kiyota

  DOI：10.1093/bbb/zbaa002

  日期：2021.1.7

  Synthesis of assumed natural (12R,13S)-enantiomers of pyriculariol (1) and dihydropyriculariol (2), phytotoxins isolated from rice blast disease fungus, Pyricularia oryzae, was achieved using Wittig reaction or microwave-assisted Stille coupling reaction as the key step. The synthesis revealed that the natural 1 and 2 are racemates. Foliar application test on a rice leaf indicated that both the salicylaldehyde core and side chain were necessary for phytotoxic activity. The fungus is found to produce optically active phytotoxins when incubated with rotary shaker, but racemic ones when cultured using an aerated jar fermenter.

  使用Wittig反应或微波辅助的Stille偶联反应作为关键步骤，合成了米瘟病菌Pyricularia oryzae分离的植物毒素pyriculariol（1）和dihydropyriculariol（2）的假定天然（12R，13S）对映体。合成表明，天然1和2是外消旋体。在水稻叶上进行叶面喷施试验表明，水杨醛核心和侧链均对植物毒性活性必不可少。当使用旋转摇床进行孵育时，真菌会产生光学活性的植物毒素，但是使用通气罐发酵器培养时则产生外消旋体。

• Nukina, Manabu; Sassa, Takeshi; Ikeda, Michimasa, Agricultural and Biological Chemistry, <hi>1981</hi>, vol. 45, # 9, p. 2161 - 2162
  作者：Nukina, Manabu、Sassa, Takeshi、Ikeda, Michimasa、Umezawa, Takeshi、Tasaki, Hisao

  DOI：——

  日期：——