Dearomatising Additions: Mechanism, Scope and Applications

平面型芳香族化合物通常价格便宜，容易获得，这使它们成为有用的起始原料，特别是如果它们可以简单地转化为非芳香族产品的话。做到这一点的反应相对较少，特别是以一种也控制形状的方式(立体选择性)。我们最近发现了一种在失去芳香性的情况下对简单的芳烃进行加成反应的方法，在这项建议中，我们寻求开发芳烃的脱芳加成，作为一种普遍有用和通用的合成方法。要做到这一点，我们将研究添加的机理。反应几乎肯定是通过含有单个未配对电子的自由基中间体进行的，因此可以用电子顺磁共振(EPR)和电子-核双共振(Endor)来研究反应途径中的中间体。使用这些和选择的其他光谱技术，我们将确定(A)反应是如何工作的，以及(B)哪些反应伙伴可能最适合用于扩大反应的范围。完成这项工作后，我们将继续将脱芳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药物)。

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).