干蠕孢菌素 | 22944-03-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 中文名称: 干蠕孢菌素
• 英文名称: siccayne
• 英文别名: 1,4-Benzenediol, 2-(3-methyl-3-buten-1-ynyl)-；2-(3-methylbut-3-en-1-ynyl)benzene-1,4-diol
• CAS: 22944-03-2
• 化学式: C₁₁H₁₀O₂
• 分子量: 174.199
• InChiKey: ZUEGEPDZNAILQJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-甲基丁-2-烯基膦酰磷酸氢酯 、 干蠕孢菌素 在 iacE encoded prenyltransferase 作用下， 生成 pestalodiol E
  参考文献：
  名称：

  异戊二烯A82775C生物合成异戊二烯基转移酶的表征和氯雌甾酮的新同源物的产生。

  摘要：

  氯普帕南宁和氯比妥内酯是植物内生真菌粉虱的新代谢产物，具有抗微生物，抗肿瘤和抗艾滋病毒的活性。根据我们以前的研究，它们的高度复杂和独特的骨架是由共分离的鼠药酸（1）和iso-A82775C（10）生成的。在这里，我们确定了10的生物合成基因簇iac，并表征了iacE编码的异戊二烯基转移酶。删除iacE消除了iso-A82775C的产生，积累了缺少异戊二烯基的双氰脲（2），并生成了四个新的氯比妥内酯（3 – 6）。化合物5和6对金黄色葡萄球菌和枯草芽孢杆菌具有抗菌作用，而5对人肿瘤细胞HeLa，MCF-7和SW480也具有细胞毒性。这些结果提供了天然的戊烯氧基环己烷生物合成的第一个遗传和生化见解，并证明了通过操纵10的生物合成基因来产生多样化同源物的可行性。

  DOI：

  10.1021/acschembio.7b01059
• 作为产物：
  描述：

  1,4-二乙酰氧基-2-溴苯 在 吡啶 、 盐酸 、 sodium hydroxide 、 四(三苯基膦)钯 、 乙基溴化镁 、 正丁胺 、 三氯氧磷 作用下， 反应 58.0h， 生成 干蠕孢菌素
  参考文献：
  名称：

  Total Synthesis of Siccayne

  摘要：

  钯催化的2-溴氢醌双(甲氧基甲基醚)与2-甲基-3-丁炔-2-醇的C-C偶联是天然产物siccayne [4-(2,5-二羟基苯基)-2-甲基-1-丁烯-3-炔]来自1,4-苯醌。

  DOI：

  10.1055/s-1990-27058

文献信息

• The Synthesis of Natural Acetylenic Compounds fromEutypa lata (Pers; F.) TUL
  作者：Eric Defranq、Thierry Zesiger、Rattaele Tabacchi

  DOI：10.1002/hlca.19930760126

  日期：1993.2.10

  The synthesis of a series of novel acetylenic compounds 1–7, isolated recently from the fungus Eutypa lata, is described. The crucial step is the coupling reaction between a protected aryl halogenide and the acetylenic chain as a cuprous acetylide (Scheme 1). A more efficient method using bis(triphenylphosphine)palladium dichloride ([Pd(PPh3)2Cl2]) as catalyst was also carried out with success.

  一系列新炔属化合物的合成1 - 7，最近从真菌中分离Eutypa LATA，进行说明。关键步骤是受保护的芳基卤化物与炔属链之间的偶联反应，即乙炔化亚铜（流程1）。还成功地使用了双（三苯基膦）二氯化钯（[Pd（PPh 3）2 Cl 2 ]）作为催化剂，效率更高。
• Biosynthesis of Biscognienyne B Involving a Cytochrome P450‐Dependent Alkynylation
  作者：Jian‐Ming Lv、Yao‐Hui Gao、Huan Zhao、Takayoshi Awakawa、Ling Liu、Guo‐Dong Chen、Xin‐Sheng Yao、Dan Hu、Ikuro Abe、Hao Gao

  DOI：10.1002/anie.202004364

  日期：2020.8.3

  The alkyne is a biologically significant moiety found in many natural products and a versatile functional group widely used in modern chemistry. Recent studies have revealed the biosynthesis of acetylenic bonds in fatty acids and amino acids. However, the molecular basis for the alkynyl moiety in acetylenic prenyl chains occurring in a number of meroterpenoids remains obscure. Here, we identify the

  炔烃是在许多天然产物中发现的生物学上重要的部分，也是现代化学中广泛使用的多功能官能团。最近的研究已经揭示了脂肪酸和氨基酸中炔键的生物合成。然而，在许多类萜中出现的炔基异戊二烯基链中的炔基部分的分子基础仍然不清楚。在这里，我们基于异源表达，饲喂实验和体外试验，鉴定了生物合成基因簇，并表征了乙炔类金属萜类双缩乙炔B的生物合成途径。这项工作表明，炔烃部分是由空前的细胞色素P450酶BisI构建的，该酶对C5和C15异戊二烯基链具有混杂活性。这一发现为发现新化合物提供了机会，
• Biomimetic Total Syntheses of (+)-Chloropupukeananin, (−)-Chloropupukeanolide D, and Chloropestolides
  作者：Takahiro Suzuki、Soichiro Watanabe、Wataru Ikeda、Susumu Kobayashi、Keiji Tanino

  DOI：10.1021/acs.joc.1c02108

  日期：2021.11.5

  highly functionalized tricyclo[4.3.1.03,7]decane or bicyclo[2.2.2]octane skeletons. Biosynthesis of the chloropupukeananin family is triggered by the intermolecular heterodimeric Diels–Alder reaction between maldoxin and iso-A82775C; however, the enzymes involved have not yet been identified. We herein report the one-pot biomimetic synthesis of chloropupukeananin and chloropupukeanolide D. Moreover,

  Chloropupukeananin、chloropupukeanolides 和 chloropestolides 是结构复杂的生物活性天然产物家族，具有高度官能化的三环[4.3.1.0 3,7 ]癸烷或双环[2.2.2]辛烷骨架。chloropupukeananin 家族的生物合成是由maldoxin 和iso-A82775C 之间的分子间异二聚体Diels-Alder 反应触发的；然而，所涉及的酶尚未确定。我们在此报告了 chloropupukeananin 和 chloropupukeanolide D 的一锅仿生合成。此外，溶剂对 siccayne 和 maldoxin 的分子间 Diels-Alder 反应的影响表明 chloropupukeananin 家族的生物合成涉及 Diels-Alderase 催化的异二聚体 Diels ——阿尔德反应。
• Synthesis of Bioactive Speciosins G and P from <i>Hexagonia speciosa</i>
  作者：Guillermo A. Guerrero-Vásquez、Nuria Chinchilla、José M. G. Molinillo、Francisco A. Macías

  DOI：10.1021/np500341q

  日期：2014.9.26

  The first total synthesis of speciosins P and G, previously isolated from Hexagonia speciosa, is reported. These compounds have been synthesized by Sonogashira coupling from readily available starting materials. Siccayne was also synthesized from the same starting material in two steps along with a number of other derivatives. The compounds were tested in the wheat coleoptile bioassay. The most active compound was the intermediate 18, followed by 29 and 17. The structural requirements for activity in these compounds are the presence of methoxy groups in the aromatic ring and a formyl or hydroxy group in the side chain.
• Synthesis and Structure−Phytotoxicity Relationships of Acetylenic Phenols and Chromene Metabolites, and Their Analogues, from the Grapevine Pathogen <i>Eutypa </i><i>l</i><i>ata</i>
  作者：Leverett R. Smith、Noreen Mahoney、Russell J. Molyneux

  DOI：10.1021/np020415t

  日期：2003.2.1

  Eutypa lata, the fungus responsible for dying-arm disease in grapevines, produces a number of structurally related secondary metabolites, of which eutypine (1) has been implicated as the principal phytotoxin. However, analysis of an E. lata strain from California known to be pathogenic to grapevines showed that eutypine was not present, suggesting that other metabolites could be phytotoxic. Investigation of the relative phytotoxicities of individual metabolites has been limited by insufficient material and lack of a reliable bioassay. Metabolites of particular interest and their precursors were therefore synthesized, and a rapid, quantitative bioassay via topical application of individual compounds to disks of grape leaves and measurement of chlorophyll loss was developed to provide a relative measure of tissue damage. The recently reported metabolite eulatachromene (2) was found to have phytotoxicity greater than that of eutypine (1). The cyclization product, 5-formyl-2-methylvinyl[1]benzofuran (3), also showed significant activity, whereas the reduction product, eutypinol (4), was inactive, as was the quinol, siccayne (5). These results indicate that before strains of Eutypa are incriminated as pathogenic they must be analyzed for the presence or absence of specific constituents for which the phytotoxicity has been unequivocally established.