Dearomatising Additions: Mechanism, Scope and Applications

脱芳香添加：机制、范围和应用

• 批准号: EP/E057780/1
• 负责人: Jonathan Clayden
• 金额: $ 16.28万
• 依托单位: University of Manchester
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2007
• 资助国家: 英国
• 起止时间: 2007 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FE057780%2F1
• 关键词: Dearomatising; Additions; Mechanism; Scope; Applications

Flat aromatic compounds are often cheap and readily available, making them useful starting materials, especially if they can be converted in a simple manner to non-aromatic products. There are relatively few reactions which do this, especially in a manner which also controls shape (stereoselectivity). We have recently discovered a way of carrying out addition reactions to simple aryloxazolines with loss of aromaticity, and in this proposal we seek to develop the dearomatising addition to aryloxazolines as a generlly useful and versatile synthetic method. To do this, we shall investigate the mechanism of the addition. The reaction almost certainly proceeds via radical intermediates containing single unpaired electrons, and the intermediates in the reaction pathway can therefore be studied by Electron Paramagnetic Resonance (EPR) and Electron-Nuclear Double Resonance (ENDOR). Using these and a selection of other spectroscopic techniques we will establish (a) how the reaction works and (b) which reaction partners might best be used to extend the reaction's scope. Having doen this we will move on to apply the dearomatising addition reaction to the synthesis of valuable bioactive compounds such as carbacyclic sugar analogues (many of which are potential antiviral agents).

扁平芳族化合物通常便宜且容易获得，使它们成为有用的起始材料，特别是如果它们可以以简单的方式转化为非芳族产物。有相对较少的反应，这样做，特别是在一种方式，也控制形状（立体选择性）。我们最近发现了一种对简单的芳基恶唑啉进行加成反应而失去芳香性的方法，在本建议中，我们试图发展芳基恶唑啉的脱芳香加成作为一种通用的和多用途的合成方法。为此，我们将研究添加的机制。该反应几乎肯定通过含有单个未成对电子的自由基中间体进行，因此可以通过电子顺磁共振（EPR）和电子-核双共振（ENDOR）研究反应途径中的中间体。使用这些和其他光谱技术的选择，我们将建立（a）反应如何工作和（B）哪些反应伙伴可能最好地用于扩大反应的范围。在此之后，我们将继续将脱芳构化加成反应应用于合成有价值的生物活性化合物，如碳环糖类似物（其中许多是潜在的抗病毒剂）。