Developing a Catalytic Strategy to Address Regiocontrol in Radical Reactions of Aromatic Heterocycles

构建具有不同取代模式的碱性杂芳烃是非常重要的，但由于与金属催化剂不相容，杂环C-H键的直接转化是一个主要挑战。迷你型加成是一种自由基加成过程，在被“亲核”自由基攻击之前，一个基本杂环被质子化，其LUMO随之降低。这是一种看似简单的方法，不需要催化剂。阻碍其广泛使用的问题是，由于C2和C4位置的LUMO系数差异不够大，对吡啶和喹啉等杂环缺乏区域选择性。我们将开发一种催化方法来添加Minisci，这将使我们能够控制C2和C4之间的区域选择性。我们预计，这一策略的成功实现将使丰富的自由基化学应用于具有新发现的区域控制的有价值的基本杂环。

Construction of basic heteroarenes with varied substitution patterns is of great importance, but direct transformation of heterocyclic C-H bonds is a major challenge, often due to incompatibility with metal catalysts. Minisci-type additions are radical addition processes in which a basic heterocycle is protonated with a concomitant lowering of its LUMO, before attack by 'nucleophilic' radicals. This is a deceptively simple method with no catalyst required. The problem that has held back its widespread use is a lack of regioselectivity on heterocycles such as pyridines and quinolines due to insufficiently different LUMO coefficients of the C2 and C4 positions. We will develop a catalytic approach to Minisci additions that will allow us to control regioselectivity between C2 and C4. We anticipate that successful realisation of this strategy will allow the wealth of radical chemistry to be applied to valuable basic heterocycles with new-found regiocontrol.