Metallocage Photoredox Confined Synergistic Catalysis on 1,3-Rearrangement Reaction

The realm of catalytic chemistry has witnessed notable advancements through the integration of photoredox confined synergistic catalysis, a method that synergizes the benefits of photoredox and confined catalysis. This innovative approach facilitates the generation of reactive intermediates via photoredox reactions, while the confined microenvironment tailors distinct selectivity processes. Despite its progress, several aspects, including the intricacies of the encapsulation process, the characteristics of the catalysis, and the underlying synergistic mechanisms, remain to be fully elucidated. In order to answer these questions, this work investigated the 1,3-rearrangement reaction mechanism of cinnamyl ammonium bromide within a metallocage (K12[Ga4L6], L = N,N′-bis(2,3-dihydroxybenzoyl)-1,5-diaminonaphthalene). Through molecular dynamics simulations, the encapsulation process was meticulously analyzed to determine the initial host–guest assembly structure. Subsequent quantum chemical calculations shed light on the mechanistic details and selectivity nuances of the 1,3-rearrangement. The investigation reveals that the radical mechanism unfolds in two pivotal stages: the breaking of the C–N bond, accompanied by an electronic state conversion facilitated by photoredox catalysis, and the formation of the C–N bond, conducted within the confined space of the metallocage. Notably, confined catalysis plays a crucial role in altering the product selectivity, demonstrating the potential of this catalytic strategy to guide the reaction pathways with enhanced precision. This study not only clarifies the operational dynamics of photoredox confined synergistic catalysis but also lays the foundation for future innovations in catalytic chemistry by highlighting the critical factors that influence reaction selectivity and efficiency.