Title: Porphyrinic Metal–Organic Frameworks Installed with Brønsted Acid Sites for Efficient Tandem Semisynthesis of Artemisinin

Abstract: Artemisinin, an essential antimalarial drug, requires a synthetic pathway that has a high environmental and financial cost. Conventional homogeneous photocatalysts and acid catalysts usually suffer from recycling problems that lead to a dramatic decrease in catalytic activity, while current heterogeneous catalysts with low surface areas are limited by issues such as active-site accessibility and precise reaction tailorability. Herein, we report the successful installation of Brønsted acid sites into a series of porphyrinic metal–organic frameworks (MOFs) that feature large channels, high surface areas, and tailored pore environments for catalysis via a postsynthetic installation strategy. Accordingly, the resulting dual-function solid acid/photocatalyst can be utilized for the tandem semisynthesis of artemisinin from dihydroartemisinic acid and demonstrates efficient catalytic performance. It is worth noting that this dual-functionalized nanoreactor acts as the most efficient catalyst for artemisinin production among all known homogeneous and heterogeneous photocatalysts. The facile heterogeneous catalytic system can be efficiently recycled, showing enhanced stability in comparison to the traditional homogeneous catalysts. The result highlights the advantage of the hierarchically porous MOF catalyst with tailored functionalities and cooperative motifs as a highly accessible and recyclable heterogeneous catalyst, providing a more efficient and recyclable approach to drug production.