Free radicals are a common type of intermediate in chemical reactions, characterized by their diverse formation methods, low reaction energy barriers, good tolerance to traditional reactive functional groups, ease of achieving polarity reversal, and the ability to rapidly increase molecular complexity through tandem reactions. Due to these characteristics, free radical-mediated reactions have become one of the important tools in organic synthesis methodology. However, the highly reactive nature of free radicals makes the reactions easy to occur but difficult to control. How to improve reaction selectivity, especially chemical and stereoselectivity, is a key challenge in the development of free radical reactions.
Supramolecular chemistry is expected to provide novel and effective solutions to the above challenges. In the enzymatic catalysis systems in nature, non-covalent interactions play a crucial role, achieving a series of highly selective conversion reactions by pre-organizing substrates, stabilizing intermediates or transition states, etc. Inspired by this, we hope to systematically investigate the regulation rules of non-covalent interactions (such as hydrogen bonding, π-π interactions, ionic pair interactions, etc.) and nanoscale confinement effects on the reactivity of free radical intermediates. Based on this, we will apply the strategies of supramolecular assembly to catalyst design, guiding free radicals to react along preconceived paths and obtaining reaction products with clear structures and stereospecificity.