Imposing Regiocontrol on Minisci-Type Additions via Non-Covalent Catalysis

构建具有不同取代方式的碱性杂芳烃具有重要意义，但杂环C-H键的直接转化是一个主要挑战，这通常是由于与金属催化剂不相容。Minisci型加成是一种自由基加成过程，在此过程中，基本杂环被质子化，并伴随着其LUMO的降低，然后再受到亲核自由基的攻击。这是一种看似简单的方法，不需要催化剂。阻碍其广泛应用的问题是，由于C2和C4位置的LUMO系数不够不同，导致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进行微小的CI加成，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基础化学的丰富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.