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

醛类化合物的合成利用在有机化学中占有重要地位。除了醛作为亲电试剂的极性反应性之外，由醛的单电子还原产生的酮基自由基是亲核的，因此提供了umpolung反应性。传统上，酮基自由基是在相对苛刻的条件下用过量的强还原剂形成的，限制了它们在净还原性反应中的应用。通过醛衍生物的机械上不同的单电子氧化的卤代烷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。本研究将探索一种在温和条件下通过光氧化还原催化氧化醛类衍生物获得酮自由基的新方法。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.