pyrinodemin A

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: pyrinodemin A
• 英文别名: (3S,3aS,6aR)-3-(8-pyridin-3-yloctyl)-1-[(Z)-14-pyridin-3-yltetradec-5-enyl]-3,3a,4,5,6,6a-hexahydrocyclopenta[c][1,2]oxazole
• 化学式: C₃₈H₅₉N₃O
• 分子量: 573.906
• InChiKey: ZRNXNRWWCKQFOL-UWPAFQDOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.7
• 重原子数：
  42
• 可旋转键数：
  23
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  38.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  5-己炔-1-醇 在 palladium on activated charcoal 正丁基锂 、 草酰氯 、 camphor-10-sulfonic acid 、 氢气 、 对甲苯磺酸 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 、 二氯甲烷 、 乙酸乙酯 、 甲苯 为溶剂， 反应 51.25h， 生成 pyrinodemin A
  参考文献：
  名称：

  （-）-pyrinodemin A的双键位置和绝对构型的总合成和分配

  摘要：

  [结构：见正文]结构上新颖的顺式环戊[c]异恶唑烷生物碱（-）-吡咯烷素A（3）的首次不对称全合成是通过高度非对映选择性的分子内硝酮-烯烃完成的，具有较强的细胞毒性。环加成反应是关键步骤。因此，发现迄今未知的嘧啶亚胺A的绝对构型如结构式3所示。

  DOI：

  10.1021/ol034700v

文献信息

• Studies toward the Total Synthesis of the Cytotoxic Sponge Alkaloid Pyrinodemin A
  作者：Jack E. Baldwin、Stuart P. Romeril、Victor Lee、Timothy D. W. Claridge

  DOI：10.1021/ol015646q

  日期：2001.4.1

  [structure: see text]. The syntheses of the proposed structure of pyrinodemin A (1) and its cis double bond positional isomer (C15'-C16') in racemic form are described. The key reaction involved an intramolecular nitrone/double bond cycloaddition. Our results suggest that neither 1 nor its double positional isomer is the correct structure of pyrinodemin A

  [结构：见文字]。描述了拟除虫菊酯A（1）及其外消旋形式的顺式双键位置异构体（C15'-C16'）的合成。关键反应涉及分子内的硝酮/双键环加成。我们的结果表明，无论是1还是它的双重位置异构体都不是嘧啶A的正确结构
• Total Synthesis and Assignment of the Double-Bond Position and Absolute Configuration of (−)-Pyrinodemin A
  作者：Yoshiki Morimoto、Satoru Kitao、Tatsuya Okita、Takamasa Shoji

  DOI：10.1021/ol034700v

  日期：2003.7.1

  see text] The first asymmetric total synthesis of a structurally novel cis-cyclopent[c]isoxazolidine alkaloid, (-)-pyrinodemin A (3), which exhibits potent cytotoxicity, has been accomplished through a highly diastereoselective intramolecular nitrone-olefin cycloaddition reaction as the key step. Thus, it has been found that the hitherto unknown absolute configuration of pyrinodemin A is as indicated

  [结构：见正文]结构上新颖的顺式环戊[c]异恶唑烷生物碱（-）-吡咯烷素A（3）的首次不对称全合成是通过高度非对映选择性的分子内硝酮-烯烃完成的，具有较强的细胞毒性。环加成反应是关键步骤。因此，发现迄今未知的嘧啶亚胺A的绝对构型如结构式3所示。
• Enantioselective total synthesis of pyrinodemin A
  作者：Annie Pouilhès、Anel Florès Amado、Anne Vidal、Yves Langlois、Cyrille Kouklovsky

  DOI：10.1039/b800840j

  日期：——

  Pyrinodemin A 1, a cytotoxic marine alkaloid, was synthesized in a convergent and enantioselective fashion. The key steps are an asymmetric intramolecular dipolar cycloaddition of an oxazoline N-oxide to introduce the bicyclic ring system of the molecule, a cuprate coupling for the extension of the saturated chain and a B-alkyl Suzuki coupling for the introduction of a 3-pyridyl moiety. Reductive amination allowed the coupling of the second side-chain onto the nitrogen atom to give 1. Additionally, attempts to prepare 1 from a trienic precursor by a double B-alkyl Suzuki reaction are described.

  Pyrinodemin A 1是一种具有细胞毒性的海洋生物碱，以一种汇聚和选择性鉴别的方式合成。关键步骤包括：将氧杂环N-氧化物进行不对称的分子内偶极环化反应，以引入分子的双环体系；通过铜盐偶联扩展饱和链；以及B-烷基铃木偶联以引入3-吡啶基部分。还原胺化反应使得第二个侧链与氮原子相连接，从而得到1。此外，还描述了通过双B-烷基铃木反应从三烯前体制备1的尝试。
• Synthesis of pyrinodemins A and B. Assignment of the double bond position of pyrinodemin A
  作者：Barry B Snider、Bo Shi

  DOI：10.1016/s0040-4039(01)00003-x

  日期：2001.2

  Condensation of aldehyde 3a with hydroxylamine 4b afforded nitrone 2, which underwent an intramolecular cycloaddition to give Ib, the proposed structure of pyrinodemin A. A similar condensation of aldehyde 3a and hydroxylamine 4a provided pyrinodemin A (1a), which has the double bond one carbon further away from the isoxazolidine. An analogous sequence gave pyrinodemin B (21). (C) 2001 Elsevier Science Ltd. All rights reserved.
• On the synthesis of pyrinodemin A. Part 1: The location of the olefin
  作者：Stuart P. Romeril、Victor Lee、Jack E. Baldwin、Timothy D.W. Claridge

  DOI：10.1016/j.tet.2004.11.051

  日期：2005.1

  The elucidation of the structure of the cytotoxic marine sponge alkaloid pyrinodemin A by synthesis is described. Based on the C-13 NMR spectra of three double bond positional isomers and the natural product, it is concluded the C14'-C15' isomer best represents the true structure of pyrinodemin A. In addition, the structural assignment of pyrinodemin C is evaluated. (C) 2004 Elsevier Ltd. All rights reserved.