Ketyl Radicals by Photoredox-Catalysed Oxidation of Redox Active Aldehyde Derivatives

醛的综合利用在有机化学中占有举足轻重的地位。除了醛作为亲电剂的极性反应性外，醛的单电子还原生成的酮基自由基也是亲核性的，因此提供了Upolung反应性。传统上，酮基自由基是在相对恶劣的条件下形成的，含有过量的强还原剂，限制了它们的应用，仅限于净还原的反应。通过醛衍生物机械上不同的单电子氧化来访问酮基自由基可以实现净氧化还原-神经转化。然而，现有的通过单电子氧化产生酮基自由基的合成策略仍然很少。在本项目中，将研究一种新的方法，通过光氧化还原催化的醛衍生物的氧化，在温和的条件下提供酮基自由基。希望这种方法将在合成和药物化学等领域引起广泛的兴趣。

Synthetic utilization of aldehydes is of pivotal importance in organic chemistry. Besides the polar reactivity of aldehydes as electrophiles, ketyl radicals generated by single electron reduction of aldehydes are nucleophilic, therefore offering umpolung reactivity. Traditionally, ketyl radicals are formed under relatively harsh conditions with an excess of strong reductants, limiting their application to reactions which are net reductive. Accessing ketyl radicals by a mechanistically distinct single electron oxidation of aldehyde derivatives can enable net redox-neural transformations. However, existing synthetic strategies to generate ketyl radicals via single-electron oxidation remain rare. In this project, a novel approach will be investigated to afford ketyl radicals under mild conditions via photoredox-catalysed oxidation of aldehyde derivatives. It is hoped that this methodology will be of broad interest in areas such as synthetic and medicinal chemistry.